JP2005313934A - Method for detecting or detecting/adjusting environment in packaging body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To detect or detect/adjust the environment in a packaging body from the outside of the packaging body. <P>SOLUTION: An adhesive label equipped with a functional part is stuck on the outside of the packaging body with an air passage so as to cover the air passage, and the functional part of the adhesive label detects the environment in the packaging body through the air passage, or detects the environment in the packaging body and adjusts the environment in the packaging body. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an environment detection or detection / adjustment method in a package using an adhesive label. In particular, it is a method for detecting, detecting or adjusting the environment inside the package with an adhesive label having a functional part from outside the package.

In addition to the conventional form of purchasing ingredients at supermarkets and cooking and eating the purchased ingredients at each home, recently there is no time for cooking due to working together, or more time for my hobbies Therefore, with respect to cooking, there has been an increase in the form of purchasing cooked foods cooked in a backyard such as a supermarket or a central kitchen and eating them at home.
On the other hand, for cooked foods at supermarkets and convenience stores, product development tailored to the taste, quantity, etc. of individual foods has been actively promoted by selling the convenience of cooked foods, and many types of foods have been put on the market. Has been. In addition, sugar beet sellers such as supermarkets and convenience stores provide delicious foods with reduced food preservatives, etc. in order to provide the delicious taste of the ingredients themselves, which is a strong consumer demand, and to respond to safety, safety and health-consciousness. We are exploring, but reducing food preservatives will accelerate the start of food spoilage, so food safety measures are essential. In addition, it is widely known that the influence of oxygen in the air is important from research on food spoilage. For this reason, various methods for packaging the package in an oxygen-free state have been studied.

For the purpose of preventing the food from decaying, as a method of keeping the package in an oxygen-free state, the package is vacuum-packed in a vacuum, or oxygen-absorbed with an oxygen absorbent in the package, A gas replacement packaging method in which a gas is sealed with a desired gas.
For example, in the case of vacuum packaging, the packaging body is kept in a vacuum state, so that it is possible to prevent the oxidation of foods due to oxygen and to determine whether the packaging body is kept in a vacuum. By visually checking whether there is an inflow, it can be determined relatively easily. Further, it is advantageous in terms of storage and display space, and is often used when relatively long-term storage is required. However, since the inside of the package is evacuated, the food is in a packaging form that is closely attached by atmospheric pressure by the film etc. that wraps the packaging, and it cannot give a sense of volume, and the form of the food becomes distorted Therefore, a problem remains from the viewpoint of cosmetics.

On the other hand, in the case of using an oxygen absorbent in the package, packaging with a packaging material having an oxygen absorption layer, or in a gas replacement packaging method that seals the package with a desired gas, the food is not crushed by atmospheric pressure, Since the food can be displayed in its shape, it is excellent in that the product can be differentiated by a so-called display effect such as making the product look delicious. For this reason, for products having a shelf life within a few days to a month, oxygen-absorbing oxygen-absorbing packaging and gas replacement packaging are mainly studied.
However, in an oxygen-free packaging method using an oxygen absorbent in the package or a gas replacement packaging method in which the package is sealed with a desired gas, a gas atmosphere suitable for the package is determined by visually observing the gas environment in the package. It is difficult to determine whether it is stored below, and a method for determining whether the gas atmosphere in the package is appropriate is being sought.

First, various gas replacement packaging methods have been conventionally studied, and a method using a film is disclosed as a representative example. For example, Patent Document 1 discloses a method in which contents are placed in a container and the whole container is covered with a film while gas replacement is performed, and the container is sealed. This method is superior in that gas replacement in the film by gas flash and hermetic packaging capable of confining the gas can be easily performed at the same time.
However, the method represented by Patent Document 1 still has problems such as whether the inside of the package can be surely replaced with gas or it is difficult to confirm whether there is no inflow of oxygen.

  As a method for confirming the environment in the package, a method for detecting the presence or absence of oxygen in the package has been conventionally performed. As such an oxygen indicator, for example, Patent Document 2 discloses a deoxygenation indicator composed of methylene blue, a saccharide, an alkaline substance, moisture, and ascorbic acid. This indicator uses methylene blue as the indicator dye, and the pH of the water in the indicator changes depending on the presence or absence of oxygen. As a result, the methylene blue is blue when there is oxygen and colorless when there is no oxygen. It is excellent in that it can be done. In addition to the oxygen indicator function consisting of methylene blue, saccharides, alkaline substances and moisture, it is also excellent in that it has a deoxygenating function with ascorbic acid.

In addition to the integrated form of oxygen indicator and oxygen scavenger, oxygen indicator consisting of methylene blue, saccharides, alkaline substances, and moisture, which has only an oxygen indicator function, is attached to oxygen scavengers (ascorbic acid or iron) on both sides. There is also a type in which an oxygen scavenger with an oxygen indicator adhered with a tape or the like is enclosed in a packaging container to check for the presence of oxygen.
However, when an oxygen indicator consisting of methylene blue, saccharides, alkaline substances and moisture represented in Patent Document 2 is packed in a sachet, the sachet moves freely in the package, so it can enter food gaps, and the sachet can be used as a seasoning, etc. There are still problems such as children and elderly people eating sachets directly or sprinkling powder in the sachets on food.
JP-A-42-1956 Japanese Patent Laid-Open No. 54-138489

  SUMMARY OF THE INVENTION An object of the present invention is to provide a package environment detection or detection / adjustment method that can detect, detect, and adjust the environment in the package from the outside of the package.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have made the present invention.
That is, the present invention is as follows.
(1) An adhesive label having a functional part is attached from the outside of a package having a ventilation path so as to cover the ventilation path, and the functional part of the adhesive label detects the environment in the package through the ventilation path or the package. A method for detecting or detecting / adjusting the environment inside the package that detects the environment and adjusts the environment inside the package.
(2) At least the functional part of the adhesive label is selected from an oxygen concentration detecting agent, an oxygen absorbent, a desiccant, a humidity control agent, an ethanol transpiration agent, a carbon dioxide generating agent, a freshness maintaining agent, a temperature detecting agent, and a humidity detecting agent. The package internal environment detection or detection / adjustment method according to (1) above, comprising one.
(3) The in-packaging environment detection or the above-mentioned (1) or (2), wherein the container or lid or packaging film or bag forming the package contains at least one of a gas barrier resin and a water vapor barrier resin Detection / adjustment method.
(4) The packaging environment detection or detection / adjustment method according to any one of (1) to (3), wherein the adhesive label contains at least one of a gas barrier resin and a water vapor barrier resin.
(5) The package environment detection or detection / adjustment method according to any one of (1) to (4) above, wherein the functional part of the adhesive label is covered with a protective film.

  The effect based on the structural requirements in the present invention, which is different from the prior art, is that the packaging environment detection or detection / adjustment method of the present invention is that the functional part of the adhesive label simply detects the environment in the packaging. If the functional unit has a function capable of controlling the environment in the package, for example, in the case of a humidity control agent, the humidity in the package can be adjusted by detecting the humidity in the package. Moreover, the adhesive label of this invention can be fixed to a package body by sticking the adhesive label which comprised the functional part from the outer side of the package body.

Hereinafter, the present invention will be described in detail with a focus on preferred embodiments thereof.
The most different point of the present invention from the prior art is that, in the case of a package that has been replaced by gas using the conventional gas replacement packaging sealing method, the environment in the package is detected or the environment in the package is detected to adjust the environment in the package. In contrast, the present invention applies an adhesive label having a functional part from the outside of the package through an air passage, so that if the functional part is an oxygen concentration detector, the presence or absence of oxygen in the package Can be detected visually by color.
In the packaging environment detection or detection / adjustment method of the present invention, the functional part of the adhesive label not only simply detects the environment in the packaging, but also the function part has a function capable of controlling the packaging environment. In the case of an agent, the humidity in the package can be adjusted by detecting the humidity in the package. Further, the adhesive label of the present invention can be fixed to the package by attaching an adhesive label having a functional part from the outside of the package, and in the case of a small bag having a detection function, which is a conventional technique, a container or a bag. Insert the sachet inside, and the sachet will move freely inside the package, so it will enter the gap between foods, misidentify the sachet as a seasoning, etc., children and elderly people eat the sachet directly, and the powder in the sachet is used as food It can solve the problem of sprinkling and eating. Furthermore, when the package is heated with a microwave oven or the like, the package can be heated without impairing the appearance of the package, and the gas in the package whose internal pressure has increased can be safely discharged.

The package as used in the present invention refers to a package in which the contents are packaged using a known packaging method such as a container, lid, tray, bag, packaging film, or a combination thereof. If there is no problem. For example, a package using a container and a lid (FIG. 6; A is an adhesive label affixed to the top of the lid, B is an adhesive label affixed to the side of the lid), and a package using a bag (FIG. 7) The contents are put into a container, covered with a lid, or the contents are put into a tray and wrapped with a bag or a packaging film.
The method for detecting the environment in the package of the present invention or adjusting the environment in the package by detecting the environment in the package includes a ventilation path in the package, and the environment in the package is provided in the adhesive label through the ventilation path. The functional part detects or detects / adjusts.

The air passage of the present invention will be described. The air passage of the present invention is a passage for detecting or detecting / adjusting the environment inside the package, and the size, shape, number, and the like are not hindered as long as the environment inside the package can be detected, detected / adjusted. More preferably, the lid is provided on the lid because the detection result can be easily confirmed from the upper surface of the package.
The air passage of the present invention has no problem even if the package body is perforated before the contents are packaged or the package body is perforated after the contents are put. There is no problem as long as the perforation method is a known method, and in the case of a package made of plastic, a method for creating a ventilation path by sharp cutting, cutting tools, melting or the like can be mentioned. In the case of packaging using a film, for example, as in Patent Document 1, heat shrinkability is imparted to the film by stretching or the like, and the packaged object is sealed and packaged with a heat shrink film by heat sealing or the like. In the technology of packaging with the method of shrinking the heat-shrinkable film with tight and packing tightly, in order to discharge the excessive gas existing in the package body outside the package body at the time of heat shrinking, a hole is made in the heat-shrinkable film and discharged However, the hole for discharging the gas may be used as the air passage of the present invention, and an adhesive label having the functional part of the present invention may be stuck on the discharge hole.

  The opening shape of the air passage of the present invention only needs to be able to detect or detect / adjust the environment inside the package. For example, the opening shape of the air passage is a square (A in FIG. 1), a rectangle (B in FIG. 1), a square (R in the corner) (C in FIG. 1), 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 shape (I in FIG. 1), indefinite shape (FIG. 1) In addition, a cutout shape having a complete opening, such as J), and other shapes that are not completely cut out are U-shaped (O in FIG. 1), V-shaped (P in FIG. 1), U-shaped (Q in FIG. 1). , C-shaped (R in FIG. 1), indentation (S in FIG. 1), and the like. These cut shapes are more preferred because there are no chips when the lid is drilled.

Furthermore, it is preferable that the number of air passages is as small as possible to reduce the complexity when closing the air passages and from the viewpoint of the cosmetic properties of the packaging container, if possible. However, even in the case of a large number of holes, if a plurality of small holes are concentrated in one place and these are closed with a single adhesive label, it can be used even if the mechanical strength of the adhesive label is small. This is preferable.
The containers and trays referred to in the present invention are containers for receiving contents having a form including a receiving container and a lid. The material may be any material as long as it can contain the contents, and examples thereof include plastic, metal, wood, paper, other simple substances, and lamination of the materials. The lid 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, other Examples thereof include a simple substance or a laminate of the materials.

  From the viewpoint of visually confirming the contents, the lid covering the upper part is preferably a transparent and glossy plastic. The bag as used in the present invention refers to a container in which an object is placed and its mouth is closed. Wrapping film refers to the contents placed in a tray, etc., wrapped with a wrapping film and sealed with heat seal etc., sealing method using impulse seal, hot blade seal etc., three-way seal method, There are a pillow seal method, an L-type seal method, etc., but there is no problem even if any method is used. The material of the packaging film may be any material as long as it can be used as a bag or packaging film, and examples thereof include plastic, metal, paper, other simple substances, or a laminate of the above materials.

The plastic in the present invention refers to a thermoplastic resin or a thermosetting resin, but any resin can be used as long as it is generally used for containers, lids, trays, bags, and packaging films. In general, resins used for containers, lids, trays, bags, and packaging films are roughly classified into thermoplastic resins and thermosetting resins.
For example, for thermoplastic resins, 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-vinyl alcohol copolymer Resin (EVOH etc.) etc. are mentioned.

  Examples of thermosetting resins include urea resins, melanin resins, xylene resins, phenol resins, unsaturated polyester resins, and the like, and examples thereof include single resins or copolymer resins. A thermoplastic resin is preferable from the viewpoint of ease of processing. For example, a polyethylene resin (HDPE, LLDPE, etc.), a polypropylene resin (PP), a polybutene-1 resin (PB), poly-4-methylpentene- Polyolefin resins (PO) including 1-series resins, ethylene-vinyl acetate copolymer resins (EVA), ethylene-methyl methacrylate copolymer resins (such as EMA), ethylene-vinyl alcohol copolymer resins Fragrances including polyolefin resin modified products (PO modified products) such as (EVOH), polyethylene terephthalate (modified) resins (PET, etc.), polybutylene terephthalate (modified) resins (PBT, etc.) Fats that contain a part of the family components or polylactic acid resins and polyglycolic acid resins Component polyester resins (PET), polyvinylidene chloride resins (PVDC), polyvinyl chloride resins (PVC) and other chlorine resins, α-olefin-carbon monoxide copolymer resins (including hydrogenated resins) , Α-olefin (ethylene, etc.)-Styrene copolymer resin (containing hydrogenated resin), ethylene-cyclic hydrocarbon compound copolymer resin (containing hydrogenated resin), polyamide resin (Ny), caprolactone resin, The resin composition selected mainly from at least one of the above may be a single layer or a multilayer of these or a laminate of a resin different from this layer, or a stretched or unstretched state composed of these resins. Polyethylene resin (particularly HDPE), polypropylene resin (PP), ethylene-vinyl alcohol Aromatic components including copolymer resins (EVOH, etc.), polyamide resins (Ny), polyethylene terephthalate (modified) resins (PET, etc.), polybutylene terephthalate (modified) resins (PBT, etc.) A polyester resin (PET) of an aliphatic component including a part or a polylactic acid resin and a polyglycolic acid resin is preferable.

For containers, lids, trays, bags, and packaging films, films and sheets having a single layer structure or a multilayer structure composed of these resins can be used. Moreover, it is preferable that it is a gas barrier plastic from a sealing viewpoint.
Further, within the range not impairing the effects of the present invention, known additives such as antioxidants, light stabilizers, antistatic agents, antifogging agents, colorants, lubricants, etc. may be mixed, or known surface treatments may be performed. For example, vinylidene chloride or the like may be subjected to gas barrier coating treatment such as corona discharge treatment, flame treatment, irradiation treatment including electrons and plasma, ion etching treatment, and the like.
Even if it contains a resin having gas barrier properties as a gas barrier plastic used in the container, lid, tray, bag, packaging film of the present invention in the present invention, or a resin layer comprising a layered inorganic substance is provided, Gas barrier properties may be imparted. For example, an inorganic substance such as silica and / or alumina may be imparted to a low density polyethylene resin layer having poor gas barrier properties by vapor deposition. Organic and inorganic composite barrier substances may also be used.

As the gas barrier properties of the above substances, the carbon dioxide gas permeation amount is 1 to 4935 ml / m ² / day / MPa, the oxygen gas permeation amount is 1 to 3948 ml / m ² / day / MPa, and the nitrogen gas permeation amount is 1 to 1481 ml / m. Those having ² / day / MPa are preferred, more preferably the carbon dioxide gas permeation amount is 1 to 4500 ml / m ² / day / MPa, the oxygen gas permeation amount is 1 to 2500 ml / m ² / day / MPa, nitrogen gas permeation The amount is from 1 to 1300 ml / m ² / day / MPa, more preferably the carbon dioxide gas permeation is from 1 to 4000 ml / m ² / day / MPa, and the oxygen gas permeation is from 1 to 1300 ml / m ² / MPa. Day / MPa, nitrogen gas permeation amount is 1 to 1000 ml / m ² / day / MPa. Even more preferably, the carbon dioxide gas permeability is 1-1000 ml / m ² / day / MPa, the oxygen gas permeability is 1-30 ml / m ² / day / MPa, and the nitrogen gas permeability is 1-250.0 ml / m ^2. / Day / MPa.

Vapor barrier property in the present invention is preferably from the viewpoint of 0.1~300g ^/ m 2 ^/ 24hr of oxygen absorbing function, more preferably 0.1~280g ^/ m 2 ^/ 24hr, more preferably 0.3~260g / m it is a ² / 24hr.
The adhesive label referred to in the present invention has a certain planar shape, and an adhesive is present on the surface in contact with the lid, and the air passage provided in the lid can be sealed (sealed) without gaps through the adhesive. Any shape can be used as long as it can be sealed so as not to dissipate the gas in the packaging container. The planar shape of the adhesive label is square (A in FIG. 1), rectangular (B in FIG. 1), and the corner is R. 1 (C in FIG. 1), 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 shape (I in FIG. 1), indefinite shape (J in FIG. 1), circle + knob (K in FIG. 1), rectangle + knob (L in FIG. 1), ellipse + knob (FIG. 1) M), square + knob (N in FIG. 1), and the like.

  Examples of the material of the adhesive label include a single layer or a multilayer structure composed of paper, a metal thin film, a resin, and the like, but it is more preferable that the adhesive label is composed of a resin that is the same material as the container. Further, it is more preferable to use a gas barrier resin from the viewpoint of preventing sparks due to collision of electrons during heating in the microwave and from the viewpoint of preventing gas dissipation. Moreover, it is preferable that the adhesive label as referred to in the present invention has a certain degree of strength from the viewpoint of preventing breakage due to piercing from the outside. In the measurement based on the Agricultural and Forestry Standard Article 10, the piercing strength is preferably 2.0 N or more, more preferably 2.5 N or more, and further preferably 3.0 N or more.

The adhesive label referred to in the present invention is roughly divided into two layers, 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, and examples thereof include plastic, metal, wood, paper, other simple substances, or lamination of the materials. It is done. The adhesive label of the present invention is preferably the above-mentioned resin generally used for containers and lids from the viewpoint of processability and separation and disposal.
Moreover, it is a film and a sheet | seat of single layer or multilayer structure comprised from these resin. In the case of a multilayer structure, there are a coextrusion method, various laminating methods, and the like as a method for forming a multilayer. The film and sheet used for the adhesive label of the present invention are more preferably materials having gas barrier properties from the viewpoint of maintaining gas displacement.

As the base layer having gas barrier properties used in the adhesive label of the present invention in the present invention, the adhesive label is provided with a resin layer having a layer of an inorganic substance even if it contains a resin having gas barrier properties. May be given. For example, an inorganic substance such as silica and / or alumina may be imparted to a low density polyethylene resin layer having poor gas barrier properties by vapor deposition. Organic and inorganic composite barrier substances may also be used.
The gas barrier property and water vapor barrier property of the adhesive label are the same as those of the container, lid, tray, bag and packaging film.

The thickness of the gas barrier substrate layer used in the present invention varies depending on the oxygen gas permeation amount of the resin used, and the above-described oxygen gas permeation amount is 1 to 1974 ml / m ² / day / MPa. It is preferable. For example, in the case of an ethylene-vinyl alcohol copolymer resin (EVOH) with a small oxygen gas permeation amount, it is possible to achieve the oxygen gas permeation amount with a few μm from the viewpoint of the oxygen gas permeation amount, Since the waist as a label is poor, sticking of the label by a label sticking machine is poor in work efficiency, and from the viewpoint of handling the label, other waist-having resins such as polypropylene resin (PP) and polyester resin It is necessary to laminate with (PET). In the case of a gas barrier base layer having a laminated structure of PP and EVOH, the oxygen gas permeation amount is preferably 1 to 1974 ml / m ² / day / MPa, and the thickness of the gas barrier base layer is the thickness of the adhesive label. From the viewpoint of 20 to 150 μm is preferable. Moreover, More preferably, it is 30-120 micrometers, More preferably, it is 35-115 micrometers.

The adhesive layer of the adhesive label referred to in the present invention will be described. First, the term “adhesion” as used in the present invention means that an adhesive label is attached to a bag, container, or lid. Adhesive strength may be selected as appropriate, and the type and amount of adhesive may be selected depending on the desired adhesive strength. Adhesive labels and bags, containers, and lids are attached even if the adhesive strength is weak. It only needs to be able to fit and seal.
Typical adhesives include solvent type, hot melt type, reactive type, etc., but there is no problem as long as they have adhesive properties, such as rubber adhesives, acrylic adhesives, vinyl ether adhesives. And an adhesive, a silicon-based adhesive, and a resin composition selected mainly from at least one of these. From the viewpoint of easily setting desired adhesive strength, rubber adhesives, acrylic adhesives, vinyl ether adhesives, more preferably rubber adhesives and acrylic adhesives are preferred. Furthermore, an acrylic adhesive is more preferable from the viewpoint of less solvent extract and less impurities.

These adhesives contain known additives such as an antioxidant, a light stabilizer, an antistatic agent, an antifogging agent, a colorant and the like within a range not impairing the effects of the present invention. Also good. In addition, in order to intentionally cause partial peeling between the gas barrier base material layer and the adhesive layer of the adhesive label of the present invention, the gas barrier base layer is preliminarily printed with silicon having a peeling effect, and the adhesive layer is You may provide what is called a falsification prevention printing which peels from a gas barrier base material layer and remains in the container, lid | cover, and bag which are to-be-adhered bodies.
Examples of the rubber-based adhesive include natural rubber mainly composed of cis-1,4-polyisoprene, synthetic rubber mainly composed of styrene / butadiene rubber (SBR), polyisobutylene and butyl rubber, or styrene / Adhesive elastomer selected from butadiene / styrene copolymer rubber (SBS), block rubber mainly composed of styrene / isoprene / styrene copolymer rubber (SIS), etc., has a molecular weight of liquid or solid at room temperature. Adhesion imparting agents such as rosin resin, terpene resin, petroleum resin, chroman indene resin, etc., which are thermoplastic resins of hundreds to about 10,000 amorphous oligomers (medium molecular weight polymer of dimer or higher), and Examples include mineral oil, liquid polybutene, liquid polyisobutylene, and a softening agent such as liquid polyacrylate.

As the acrylic adhesive, for example, a main monomer that gives adhesiveness typically represented by a homopolymer having a low Tg, an acrylic ester of a lower alkyl group, an acrylic ester of a lower alkyl group, an alkyl methacrylate, vinyl acetate, styrene, Comonomer that can be copolymerized with main monomers such as acrylonitrile and gives cohesive properties that increase Tg, carboxyl group-containing monomers such as acrylic acid and methacrylic acid (such as acrylate), and adhesion such as hydroxyl, epoxy, and amino groups In some cases, the adhesive reaction product of the functional group-containing monomer serving as a crosslinking point may be blended with the above-described adhesion-imparting agent, softener and the like.
Examples of vinyl ether adhesives include homopolymers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and copolymers with acrylates (adhesive elastomers), and in some cases, the above-described adhesion-imparting agent and softener are blended. Things.

Examples of the silicon-based adhesive include, for example, a polymer having a residual silanol group (SiOH) at the end of a polymer chain represented by high molecular weight polydimethylsiloxane or polydimethyldiphenylsiloxane (or an adhesive elastomer) and the above-described adhesion imparting agent. Some of them contain softeners.
Adhesive strength can be set widely from the viewpoint of gas barrier properties, particularly gas replacement packaging, and acrylic, rubber and silicone adhesives are preferred from the viewpoint of food hygiene.
The adhesive strength in the present invention is preferably 0.1 to 10 N / cm in the measuring method by the 180-degree peeling method of JIS-Z-0237, from the viewpoint of the adhesive strength at the time of adhesion and the peel strength at the time of peeling. More preferably, it is 0.2-9.5 N / cm, More preferably, it is 0.3-7.5 N / cm.

Although the thickness of the adhesive layer used in the present invention varies depending on the adhesive used, the adhesive strength may be 0.1 to 10 N / cm and does not depend on the thickness of the adhesive layer. For example, in the case of an acrylic adhesive, the thickness of the adhesive layer is preferably 3 to 50 μm from the viewpoint of adhesive strength. Moreover, More preferably, it is 5-40 micrometers, More preferably, it is 8-35 micrometers.
The gas barrier adhesive label of the present invention may be provided with a knob to impart easy opening. For example, the gas barrier adhesive label is provided with a semicircular knob, and it is easier to open by pulling up the knob from the lid. More preferred. Also, by using an acrylic emulsion as the pressure sensitive adhesive for the label, the adhesive strength of the pressure sensitive adhesive is weakened by water vapor from the contents when the package is heated, and a part of the label is automatically formed by the internal pressure in the package. It may be opened to prevent bursting.

  In the protective film of the present invention, when the function and contents for transmitting the environment in the package to the functional part are foods, to ensure safety by isolation so that the functional part does not contact the contents directly. Preferably, for example, when the functional part is an oxygen detector and an oxygen absorber, the protective film can be isolated by a film body such as metal or paper in addition to a commonly used resin film. However, from the viewpoint of oxygen detection concentration, oxygen detection rate, oxygen absorption amount, oxygen absorption rate, etc., a resin film in which oxygen permeability is easy to set for a while is preferable, oxygen permeability and water vapor permeability. Can be selected as necessary. For example, when it is desired to check the presence or absence of oxygen at low oxygen, it is better to use a resin film having a high oxygen permeability and as thin as possible. The resin film that can be used in the present invention may be a single layer or multiple layers, and the resin used may be selected depending on the desired oxygen concentration.

  For example, polyolefin resins (PO) including polyethylene resins (HDPE, LLDPE, etc.), polypropylene resins (PP), polybutene-1 resins (PB), poly-4-methylpentene-1 resins, or Modified polyolefin resin (PO) including ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl methacrylate copolymer resin (EMA, etc.), ethylene-vinyl alcohol copolymer resin (EVOH, etc.) Modified product), polyethylene terephthalate-based (modified) resin (PET, etc.), polybutylene terephthalate-based (modified) resin (PBT, etc.) and some other aromatic components, or polylactic acid-based resin, polyglycol Polyester resin (PEST) of aliphatic component including acid resin, polyvinyl chloride Den resin (PVDC), polyvinyl chloride resin (PVC) and other chlorine resins, α-olefin-carbon monoxide copolymer resin (including hydrogenated resin), α-olefin (ethylene, etc.)-Styrene co Resin composition selected mainly from at least one of polymer resin (containing hydrogenated resin), ethylene-cyclic hydrocarbon compound copolymer resin (containing hydrogenated resin), polyamide resin (Ny), caprolactone resin, etc. Examples thereof include a single layer or a multilayer of these, or a laminate of a resin different from this layer, or a stretched (including shrinkable film) or unstretched resin film made of these resins.

Further, the moisture permeability is preferably from the viewpoint of 0.1~300g ^/ m 2 ^/ 24hr of oxygen absorbing function of the protective film of the present invention, more preferably 0.1~280g ^/ m 2 ^/ 24hr, more preferably 0.3 It is -260g / m < ² > / 24hr. Furthermore, the thickness of the protective film of the present invention is preferably 3 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 70 μm, from the viewpoint of mechanical waist and handling when it is made by a machine.
Further, when the protective film has a heat shrink layer, it plays a role of preventing the adhesive label from completely closing the air passage again by its own weight after the heat treatment in a microwave oven or the like by deforming the adhesive label. That is, since the adhesive label of the present invention has at least a part of the heat shrink layer, when the heat treatment is performed in a microwave oven or the like, moisture contained in the contents of the container or bag is vented as water vapor to the outside of the container or bag. The adhesive label is deformed due to the heat from the water vapor being transferred to the heat-shrinkable layer of the adhesive label, and the deformed adhesive label is reheated by the dead weight of the adhesive label after heat treatment. It is possible to prevent the container or bag from being completely closed. Therefore, the container or bag can be prevented from being dented or crushed at atmospheric pressure due to the reduced pressure in the container or bag.

The heat-shrinkable layer referred to in the present invention does not hinder wherever it is placed on the adhesive label, but it is preferable to place it on a portion near the surface layer of the adhesive label from the viewpoint of ease of heat shrinkage and its effect, and more preferably Is preferably disposed on the outermost surface of the adhesive label, more preferably on a layer adjacent to the adhesive label adhesive surface.
Since the heat shrink layer function expression of the present invention utilizes water vapor generated during heating of a microwave oven or the like, the heat shrink start temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, more preferably 90 ° C. or higher. . Such heat-shrinkability is usually imparted by stretching, but the stretching method is not affected by any known method such as a tenter type or bubble type, and all adhesive labels are stretched. Even if it is, there is no problem even if a stretched film is bonded to at least a part of the adhesive label. The bonding method of the present invention does not hinder any known method such as dry lamination, sand lamination, melt lamination, and adhesive bonding.

In addition, the shrinkage rate differs depending on where the heat-shrinkable layer is provided on the adhesive label, but preferably a shrinkage rate that can be deformed to the extent that the entire surface of the adhesive label does not adhere to the container again after the microwave heating, For example, FIG. 2 is shown as an example of a preferred embodiment of the present invention. FIG. 2 shows a functional part having a function as an adhesive of an adhesive label by applying an adhesive layer of 25 g / m ² as an adhesive layer to polyethylene terephthalate (thickness 75 μm) where the adhesive label does not shrink as a base material layer. It is the adhesive label with a function part which adhere | attached using the adhesive bond layer of the adhesive label by using as a protective film the heat-shrink film which is a heat-shrink layer so that the function part may be covered. The protective layer of the heat-shrinkable film, which is a heat-shrinkable layer, is a case where a stretched polystyrene film (thickness 25 μm) is used, and the stretched polystyrene film of the heat-shrinkable layer is shrunk by water vapor ejected from the container. Polyethylene terephthalate bends to the heat shrinkable layer side, and it is possible to prevent the terephthalate from adhering to the container due to the bend.

However, if this bending is excessive, it may be difficult to re-seal the air passage after cooling it with fingers.If you want to re-seal after cooling, this bending adjustment will reduce the shrinkage rate of the heat-shrinkable layer. It becomes important to adjust by controlling. In the form illustrated in FIG. 2, the shrinkage ratio of the stretched polystyrene film at 90 ° C. is MD direction / TD direction = 3% / 3%. The shrinkage rate is not necessarily the same in both the MD direction and the TD direction, and is preferably anisotropic from the viewpoint of the deformed shape when contracted, preferably MD / TD (or TD / MD). Is 1.1 or more, more preferably 1.3 or more.
Furthermore, even if the adhesive label itself of the present invention is not heat-shrinkable, it can be applied by bonding a heat-shrinkable film through an adhesive of the adhesive label, or by water vapor generated by heat treatment such as a microwave oven. There is no problem if the adhesive label is deformed. Thus, the heat-shrinkable layer may be used as a protective film for the functional part. The functional part is a liquid having a function, and it is preferable to make the functional liquid in some solid form from the viewpoint of handling. Therefore, it is preferable that the functional liquid is supported on a support, and examples of the support include plastic, metal, ceramic, crystalline cellulose, gel, paper, and the like. The form apply | coated to these, the form coated on the surface, and the form immersed in are mentioned.

  For example, when plastic is used as the support, it is possible to use a structure in which an oxygen unreacted solution having an oxygen indicator function is put in plastic, a structure impregnated in a porous plastic structure, or a sheet like a nonwoven fabric. Examples include water-absorbed structures. In addition, when crystalline cellulose (for example, manufactured by Asahi Kasei Co., Ltd., trade name: Avicel), gel, or paper is used as the support, it is included in a tablet-molded product, gel such as gelatin or agar, or water absorption. Can be used as long as it can be treated as a solid without inhibiting the light absorption wavelength change reaction of the enzyme. .

  The support of the present invention is preferably plastic, ceramic, crystalline cellulose, gel, paper, more preferably plastic, crystalline cellulose, gel, paper or filter paper, more preferably crystalline cellulose, gel, paper or filter paper. It is. Further, it may be printed on plastic, paper, filter paper or the like, and there is no problem if a known method is used as a printing method. Examples include gravure printing, letterpress printing, offset printing, silk screen printing, stencil printing, flexographic printing, and the like. Furthermore, visual effects such as printing may be applied to the adhesive label of the present invention in order to differentiate it from other products. It is preferable that a part of the label has a transparent part, and in order to confirm the functional part of the adhesive label, only the functional part part is not printed or is transparent enough to confirm discoloration, that is, a haze of 10 or less is preferable. . More preferably, it is 8 or less, More preferably, it is 6 or less.

  The functional unit of the present invention will be specifically described. The functional unit of the present invention is to visually detect and instruct the internal environment of the container or bag, and examples thereof include the gas environment, temperature and humidity in the container or bag. For example, when an oxygen concentration in a container or a bag is detected and instructed, an oxygen reduction indicator such as methylene blue or an enzyme detection solution using an enzyme and a substrate is impregnated into a support such as a filter paper as a functional liquid. As the detection agent, the oxygen concentration in the container or bag can be detected and instructed. In the case of a functional liquid using a redox indicator, the redox indicator referred to in the present invention only has to change the light absorption wavelength by oxidation or reduction of a substance, and the presence or absence of oxygen can be detected by detecting the changed light absorption wavelength. It can be judged.

  The wavelength range of the light absorption wavelength that can be used can be any wavelength as long as the changed wavelength can be measured or detected. For example, if there is a change region in the UV region, it may be detected using a UV measurement device. Preferably, in the visible light region (wavelength 400 to 600 nm), it can be visually confirmed without using a wavelength measuring machine. Good for. The light absorption wavelength change reaction of the oxidation-reduction indicator referred to in the present invention means that the light absorption wavelength changes due to the structural change of the oxidation-reduction indicator itself or the reaction of the oxidation-reduction indicator with another compound contained in the oxygen detector part. That means. The light absorption wavelength change reaction of the redox indicator is reversible or irreversible, but there is no problem. However, since it can be used repeatedly many times, the reversible reaction is good.

In addition, by selecting various oxidation-reduction indicators used in the present invention, it is possible to detect the presence or absence of oxygen at a desired color and a desired oxygen concentration, and further to set the oxygen concentration to be detected, the color change rate, etc. Can be set.
Furthermore, when the color change by the oxidation-reduction indicator of the present invention is an irreversible reaction, the degree of exposure due to the oxygen concentration of the content in the package can be determined by the color difference (color shade, color change, etc.), so how much content is in the package It is possible to display the total number of exposures depending on the oxygen concentration. If the discoloration by the redox indicator is in the visible light region (wavelength 400 to 600 nm), it is preferable because it can be visually confirmed at a glance without using a wavelength measuring machine.
Furthermore, when the reaction of the redox indicator is chemically stable in a mixture of several species and the reaction is independent, for example, the oxygen concentration necessary for the reaction of the redox indicator, the reaction rate, and the color during the reaction. When several different types of redox indicators are used in combination, the color can be changed stepwise depending on the oxygen concentration, such as orange at a certain oxygen concentration and blue when the oxygen concentration is high, It is possible to change the color stepwise depending on the oxygen exposure time such as brown when the exposure time is short and red when the exposure time of oxygen concentration is long.

  As the redox indicator in the present invention, methylene blue, galocyanine, methyl red, methyl bio red, thymol blue, anthocyanin, methyl yellow, phenol red, thymolphthalein, azaline yellow, anthraquinone, safranine, β-carotene, lycopene, resorufin, thionine , Cresyl blue, toluidine blue, methyl orange, litmus, bromthymol blue, carmine, phenol phthalene, etc., preferably methylene blue, methyl red, methyl bio red, thymol blue, anthocyanin, methyl yellow, phenol red, anthraquinone, Safranine, β-carotene, resorufin, thionine, cresyl blue, methyl orange, litmus, bromthymol blue, pheno Ruphthalene, more preferably methylene blue, methyl red, thymol blue, anthocyanin, phenol red, anthraquinone, β-carotene, cresyl blue, methyl orange, litmus, bromthymol blue, phenol phthalene, even more preferably methylene blue, methyl red, anthocyanin, Anthraquinone, β-carotene, methyl orange, litmus, bromthymol blue, and phenolphthalene.

In addition, the redox indicator used in the present invention is discolored by the redox function with respect to oxygen, but this function may also function with carbon dioxide. In addition to being used as an oxygen detector detector, the carbon dioxide detector May be used as
In the case of an enzyme and an enzyme detection solution using an enzyme and a substrate, the enzyme of the present invention is a high-molecular substance that acts as a catalyst for various chemical reactions carried out in the living body, and is oxidized depending on the type of reaction to be catalyzed. An enzyme that catalyzes a reduction reaction (oxidase), an enzyme that catalyzes the transfer of a functional group (transferase), an enzyme that catalyzes a hydrolysis reaction (hydrolase), an enzyme that catalyzes an elimination reaction and an addition reaction (lyase), an isomerization reaction It is classified into an enzyme (isomerase) that catalyzes ATP, an enzyme (ligase) that catalyzes a synthesis reaction that couples two molecules by coupling with hydrolysis of ATP and the like.

Originally, enzymes are responsible for catalyzing these reactions in the living body in order to maintain the living body, but the enzymes used in the present invention are enzymes or substrates depending on the presence or absence of oxygen in these enzymatic reactions. It is sufficient that the light absorption wavelength changes, and the presence or absence of oxygen can be determined by detecting the changed light absorption wavelength. The wavelength range of the light absorption wavelength that can be used can be any wavelength as long as the changed wavelength can be measured or detected.
For example, if there is a change region in the UV region, it may be detected using a UV measuring device. Preferably, the visible light range (wavelength of 400 to 600 nm) is good because it can be visually confirmed without using a wavelength measuring machine. In addition, oxygen detectors using the light absorption wavelength reaction of enzymes do not affect the enzyme reaction that determines the presence or absence of oxygen, even when carbon dioxide and alcohol are present in the package. The presence or absence of oxygen can be confirmed by a change in the light absorption wavelength (by color in the visible light range).

  The change in the light absorption wavelength may be caused by the structural change of the enzyme itself, or may be caused by the structural change of the substrate due to the enzyme reaction. As an example of a change in the structure of the enzyme itself, in the case of an enzyme having a metal (copper enzymes), the metal (copper) is in an ionic state in the system by removing a part of the metal (copper) constituting the enzyme. Since it exists, it exhibits a color (blue) peculiar to the metal ion. Examples of changes in the structure of a substrate by an enzymatic reaction include removing a hydrogen from a hydroxyl group or amino group constituting the substrate to form a double bond or exhibiting a color when the substrates associate with each other. . When the light absorption wavelength changes due to the structural change of the substrate due to the catalytic action of the enzyme, it is possible to detect the presence or absence of oxygen in the desired color by variously selecting the enzyme and the substrate, and to set the oxygen concentration to be detected and The discoloration speed and the like can be set to a desired setting.

Further, when the substrate change due to the enzyme reaction is an irreversible reaction, for example, the light absorption wavelength of the substrate itself is changed due to the structural change of the substrate in the enzyme reaction, and this change is irreversible and in the visible light region, the packaging Since the degree of exposure of the contents in the body to oxygen can be visually discriminated by color difference (color shade, discoloration, etc.), it can be integrated and displayed how much the contents in the package have been exposed to oxygen. Furthermore, even if various substrates exist simultaneously, since the enzyme reaction is independently performed between the enzyme and the substrate, several types of enzymes and substrates can be used in a mixed state.
For example, if you use a mixture of several kinds of substrates with completely different oxygen concentration, reaction rate, and color at the time of reaction in one enzyme, yellow at a certain oxygen concentration, and even higher oxygen concentration It is possible to change the color stepwise depending on the oxygen concentration, such as blue, or when the oxygen exposure time is short, brown, when the oxygen exposure time is long, the color changes stepwise depending on the oxygen exposure time, such as red. It is possible.

Examples of enzymes that change the light absorption wavelength include oxidase systems, catalase and peroxidase systems, flavin monooxygenase systems, copper hydromonooxygenase systems, iron monooxygenase systems, ribulose diphosphate oxygenase systems, and dioxygenase systems. Specifically, catechol oxidase (EC 1.10.3.1), laccase (EC 1.10.3.2), bilirubin oxidase (EC 1.3.3.5), Ascorbic acid oxidase (EC 1.10.3.3), 3-hydroxyanthranilic acid oxidase (EC 1.10.3.5) and the like can be mentioned. When present, this includes all enzymes that significantly accelerate the light absorption wavelength change reaction. These may be used alone or in combination.
The substrate may be any substrate as long as the structure is changed by the above-described enzyme and the light absorption wavelength is changed. As an example, a compound having a relatively high functional group such as a hydroxyl group, an amino group, a cyano group, and a carbonyl group is good. Bentonediol, hydroquinone, polyphenol, phenylenediamine, ascorbic acid, cyanine dye, L-ascorbate, Examples include aminophenol. For example, a redox reagent may be used as the substrate, and examples thereof include phenol derivatives, aniline derivatives, toluidine derivatives, benzoic acid derivatives, and the like.

  Specific examples include N, N dimethylaniline, N, N diethylaniline, 2,4 dichlorophenol, N-ethyl-N- (2-hydroxy-3-sulfopropyl) -3,5-dimethoxyaniline (DAOS). N-ethyl-N-sulfopropyl-3,5-dimethylaniline (MAPS), N-ethyl-N- (2-hydroxy-3-sulfopropyl) -3,5-dimethylaniline (MAOS), N-ethyl- N- (2-hydroxy-3-sulfopropyl) -m-toluidine (TOOS), N-ethyl-N-sulfopropyl-m-anisidine (ADPS), N-ethyl-N-sulfopropylaniline (ALPS), N -Ethyl-N-sulfopropyl-3,5-dimethoxyaniline (DAPS), N-sulfopropyl-3,5-dimethoxyaniline (HD APS), N-ethyl-N-sulfopropyl-m-toluidine (TOPS), N-ethyl-N- (2-hydroxy-3-sulfopropyl) -m-anisidine (ADOS), N-ethyl-N- ( 2-hydroxy-3-sulfopropyl) aniline (ALOS), N- (2-hydroxy-3-sulfopropyl) -3, 5-dimethoxyaniline (HDAOS), N-sulfopropyl-aniline (HALPS), o-dianisidine , O-tolidine, 3, 3 diaminobenzidine, 3, 3, 5, 5-tetramethylbenzidine, N- (carboxymethylaminocarbonyl) -4, 4-bis (dimethylamino) biphenylamine (DA64), 10- ( Carboxymethylaminocarbonyl) -3,7-bis (dimethylamino) phenothiazine (DA67), 3, 5-dinitrobenzoic acid, 5-aminosalicylic acid, 3-hydroxyanthranilic acid, 3,5-diaminobenzoic acid and the like, 4-aminoantipyrine, o-phenylenediamine, 1-amino-2-naphthol-4-sulfone Acid, 1-phenyl-3-methyl-5-pyrazolone, 2-amino-8-naphthol-6-sulfonic acid, 3-methyl-2-benzothiazolinone hydrazone, 2-amino-phenol-4 -Sulfonic acid, 2,6-dibromo-4-aminophenol, 2,2'-azinol- (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, 2,2'-azinobis (3- Ethylbenzothiazoline-6-sulfonic acid) ammonium salt (ABTS), catechol, tannin, epicatechin, epigallocatechin and the like.

  In addition, in the case of further fluorescent observation, a compound that fluoresces upon oxidation, such as homovanillic acid, 4-hydroxyphenylacetic acid, tyramine, paracresol, diacetylfluorescin derivative, etc. However, the substances shown here are merely examples, and all substances that significantly promote the light absorption wavelength change reaction when an enzyme is added and reacted with oxygen are included in this. Further, the light absorption wavelength may be adjusted by coupling another compound to the substrate. In addition to substrates such as 4AP, 2,6-dibromo-4-aminophenol and ABTS, when phenol, 4-hydroxybenzoic acid, etc. are allowed to coexist and an enzyme is allowed to act, a light absorption wavelength reaction occurs in the visible light region, resulting in a color tone. You can also select different colors depending on the type of substrate.

In addition, if you want to change the light absorption wavelength change reaction by the enzyme more drastically than the threshold value of oxygen concentration, or if the light absorption wavelength change reaction is caused by the presence of oxygen, and the sensitivity is too high as an oxygen detector, By coexisting an antagonist such as an inhibitor, a substrate analog or a reducing agent, the light absorption wavelength change reaction can be delayed or the sensitivity can be lowered.
Inhibitors include azide, diethyldithiocarbamic acid, thiosulfate, fluoride, cyanide, PCMB, EDTA, divalent and trivalent metals, and substrate analogs include D-amino acids and 3,5-dinitro. Examples of the reducing agent such as benzoic acid and thiosalicylic acid include dithiothreitol, cysteine, glutathione, mercaptoethanol, potassium ferricyanide, hydrogen iodide, sodium thiosulfate, aldehyde, sugar, formic acid, oxalic acid, etc. What is shown is only an example, and the types and concentrations may be used in appropriate combinations.

Furthermore, since the above-described redox indicators, enzymes, and enzyme detection solutions using enzymes and substrates consume oxygen in the reaction system, they can also be used as oxygen absorbers. It is possible to become an oxygen absorbent by using a simple reaction. Thus, the functional part of the present invention is impregnated with a functional liquid having a function to provide a humidity control agent (wet ores such as silica and talc having pores), an ethanol transpiration agent (similar to a humidity control agent, ore alcohol) It is possible to easily introduce functions such as a carbon dioxide gas generating agent into the adhesive label.
The functional part of the present invention mainly indicates a part containing a functional liquid, but it is functional even if other substances (for example, acid / alkali adjusting agent, stabilizer, other colorant (for example, food red), etc.) are included in the support. If there is no problem, there is no problem.

The gas replacement referred to in the present invention will be described. Gas replacement as used in the present invention means packaging in which air in a sealed container is replaced with a desired gas, and includes effects such as improvement in storage stability of the contents and appearance of the product color, such as food (1) Prevention of oxidation of fat and oil components, (2) Preservation of active ingredients such as vitamins, (3) Prevention of decay due to growth of fungi, fungi and yeast, (4) Dye This is effective in preventing discoloration and fading of the fragrance, and (5) preventing the fragrance from scattering. Further, the preservation of the contents may be further improved by substituting with a gas having antibacterial action such as carbon dioxide gas.
Any gas may be used as long as it is a generally known gas. 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 thereof. Further, ozone or natural and synthetic antibacterial substances (for example, hinokitiol) generally known for the purpose of sterilizing fungi, fungi and yeasts may be used positively.

Any gas replacement method may be used as long as gas replacement can be performed. Generally, a gas flush method, a nozzle method, and a chamber method are exemplified. The gas flush method is a method of replacing air in a container or bag by gas flushing a desired gas into the container or bag. The nozzle method is mainly used for replacing the gas in the bag. The nozzle is placed in the bag, the air in the bag is degassed from the nozzle, and then the desired gas is put into the bag from the nozzle. It is a method of introducing and replacing.
Furthermore, with the chamber system, a container or bag containing contents is placed in a certain space (chamber), the inside of the chamber is evacuated, and then a desired gas is introduced into the chamber to replace the gas in the container or bag. Is the method. These methods may be freely selected depending on the speed, cost, replacement rate, and the like.

Also in deaeration packaging that sucks and degass the gas in a container or bag, the gas in the container or bag is replaced with a desired gas in order to control the composition of the gas remaining in the container or bag. Suction deaeration is preferred.
As the gas composition in the container or bag, when the content is food, carbon dioxide having an antibacterial action can be used as one of the composition components in order to prevent the food from being spoiled. The component ratio of carbon dioxide is preferably 3% or more from the effect of bacteriostatic action, and may be 100%. Moreover, in order to prevent the food from decaying, alcohol having a bactericidal action may be used as one of the gas components. The component ratio of the alcohol is preferably 0.5% or more from the effect of bactericidal action, and may be contained up to a saturated vapor state. Alcohol here refers to a compound in which a hydrocarbon hydrogen atom is substituted with a hydroxyl group, such as 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, propanol, and still more preferably ethanol.

  Examples of the contents of the present invention include foods. In addition to fresh fish, raw meat, and raw vegetables called fresh three products, for example, side dishes (boiled, grilled, steamed, and fried) sold at supermarkets and convenience stores. And lunch boxes. Further, in addition to the food packaging related to the above, it may be used for any application where it is necessary to check the presence or absence of oxygen in the sealed space. For example, packaging of metal parts such as precision machine parts packaging and screws. In addition to packaging of electric parts such as electronic boards, it can be used for pharmaceuticals, cosmetics and the like.

<1. How to make adhesive labels>
1-1 Basic Adhesive Label An adhesive label was prepared using the adhesive layer shown in Table 1 as the base material layer of the adhesive label having the layer structure and thickness shown in Table 1. The functional part was stuck using the adhesive of the produced adhesive label, and further, the protective film (22 mmφ) shown in Table 1 was covered and stuck using the adhesive of the adhesive label. (Base material layer: 35 mmφ, adhesive layer application amount: 25 g / m ² )
1-2. Creation of adhesive label with function 1-2-1 Creation of adhesive label with oxygen detector function 1
Enzyme (ascorbate oxidase) and substrate (2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS)) were degassed as solvent (100 ppm of oxygen concentration 0 ppm) In an acetic acid-sodium acetate buffer solution (adjusted to pH = 4.0) at a concentration of 80 U / ml of enzyme solution and 4 mg / ml of substrate solution, respectively, to prepare a pre-prepared enzyme solution and a pre-prepared substrate solution. These preconditioned enzymes and substrate solutions were mixed in an oxygen-free atmosphere glove box to prepare a functional solution.
As shown in FIG. 2, a filter paper 5 mmφ having a thickness of 180 μm is bonded to the center of an adhesive label (material: PET thickness 75 μm, 35 mmφ, acrylic (AC) adhesive 25 g / m ² ), and a functional liquid is applied to the filter paper. 2.8 μl was applied, the center was aligned, and the filter paper was covered with a heat shrinkable layer and protective film material (OPS thickness: 25 μm, 22 mmφ) to prepare an adhesive label. This adhesive label was attached to a separator (PET / AL / PET 3 layer) in which an aluminum foil was coated with PET. Storage was performed by winding 1000 adhesive labels in a state of being attached to a separator, sealing the barrier film with a deoxidizer together with nitrogen in a roll state, and storing in a light-shielded state (5 ° C.).

1-2-2 Preparation of adhesive label with oxygen detector function 2
A known methylene blue oxygen indicator (paper type) was used as a functional part, and the adhesive label and the heat-shrinkable layer / protective film similar to 1-2-1 were used.
1-2-3 Preparation of adhesive label with desiccant function Adhesive label and heat shrinkage similar to 1-2-1 using known silica gel (grain type) as functional part (1-2-1 filter paper + alternative to functional liquid) It was created using a layer and protective film.
1-2-4 Preparation of Adhesive Label with Humidity Control Function Using a known humidity control agent (powder type: silica-based powder) as a functional part (1-2-1 filter paper + functional liquid alternative) 1-2 1. It was prepared using the same adhesive label and heat shrink layer / protective film.

<2. How to make a container (body, lid, adhesive tape)>
2-1. Main body A polypropylene resin sheet (PP) with a filler formed by dry laminating a co-pressed film of LL / NY / EVOH / NY (thickness 50 μm) was used (FIG. 3).
2-2. Lid An OPS sheet (thickness: 250 μm) formed by dry laminating a co-pressed film (thickness: 50 μm) of LL / NY / EVOH / NY was used. After the molding, using the intermediate pon of the molding machine, the top surface of the lid was punched out to 20 mmφ, and then the periphery of the molding lid was punched out to create a lid (FIG. 4).
2-3. Adhesive tape An unstretched nylon (thickness 30 μm) was coated with an acrylic adhesive at 25 g / m ² , slit to a width of 10 mm and wound around a paper tube.

<3. Actual packaging test method>
A 20 mmφ hole was opened on the top of the glove box adjusted to the mixed gas composition shown in Table 1 from a separator (PET / AL / PET 3 layer) in which an aluminum foil was coated with an adhesive label and an adhesive label with an oxygen absorbent. The container containing the lid and contents was sealed with adhesive tape, and the adhesive label peeled off from the separator coated with aluminum foil on the top surface of the hole was adhered from the outside of the lid, and the sealed container (FIG. 5). The color development time and oxygen concentration were measured for a while (storage temperature: 20 ° C., volume in container: 500 cc, contents: oil clay (200 g)).

<4. Each physical property evaluation method>
4-1. Moisture permeability was performed according to JIS-Z-0208. (40 ° C-90% RH)
4-2. Oxygen permeability It was performed according to ASTM-D-3985. (20 ° C-60% RH)
4-3. Measurement of oxygen and carbon dioxide composition ratio in the packaging container space Oxygen and carbon dioxide concentration meter (trade name: Checkpoint, manufactured by PBI Dancerson Co., Ltd.) was used to measure oxygen in the packaging container space at 20 ° C. . The nitrogen concentration was calculated from the oxygen concentration and the carbon dioxide concentration from 100%.

4-4 Temperature and humidity measurement 4-4-1. Storage temperature measurement The temperature was measured using a button type temperature measuring device (trade name: button type cool memory, manufactured by Sanyo Electric Co., Ltd.). (Adhesive label storage temperature 5 ° C, evaluation storage temperature 20 ° C)
4-4-2. Humidity measurement A small hygrometer (Asone's Ondori RH (trade name)) was enclosed in the package, and the display was recorded. After the experiment was completed, the humidity was confirmed on a personal computer, and the measured value was obtained.
4-5. Adhesive strength Measured by 180 degree peeling method of JIS-Z-0237. The outline of the measurement method is shown below. A label having a width of 25 mm was affixed to a stainless steel plate, and the force required to peel one end of the label from the test plate in a 180-degree direction at a peeling speed of 300 m / min toward the other end was defined as the adhesive strength.
4-6. Measurement of heat shrinkage rate and heat shrinkage start temperature A sample piece (50 mm square in each of MD and TD directions) is immersed for 3 minutes in silicon oil set to a predetermined temperature, and then the length of each side of the heat shrunk sample piece is measured. Measurements were made to calculate the shrinkage at that temperature. The temperature at which the shrinkage rate was 3% or more was defined as the shrinkage start temperature.

<5. Actual packaging test method>
Using a polypropylene resin sheet containing a composite filler and a composite polystyrene sheet, it was molded into the shape shown in FIG. 3 (main body) and FIG. 4 (lid), and each flange was sealed with an adhesive tape (FIG. 5). The inside of the container is replaced with a gas with the gas composition shown in Table 1 through an air passage (gas replacement hole: see FIG. 4), and the air passage of the container is sealed with an adhesive label having a layer structure shown in Table 1. did. Thereafter, measurement of the oxygen composition ratio in the container, observation of the ability of the oxygen detecting agent provided in the adhesive label, and heat treatment were performed in a microwave oven (power 1600 W), and the observation was performed.

Evaluation Criteria ◎: The functional part exerts functional capability, and after heating the microwave oven, the internal pressure rises as the temperature of the contents rises, the adhesive label peels off, and the internal pressure is released safely. It is possible to prevent the package from bursting and scattering the contents. Also, after the microwave oven heat treatment, take out the package, observe whether the adhesive label blocks the air passage by its own weight, and the adhesive label arcs inward due to the shrinkage of the heat shrink layer (protective film) Warps and does not completely block the air passage. In addition, when the package is cooled to some extent, if the arc-shaped adhesive label is re-sealed with a finger, it can be resealed with the adhesive force of the adhesive layer of the adhesive label.
X: After microwave oven heating started, the internal pressure increased with the temperature rise of the contents, and the package burst with an explosion. Also, after the microwave oven heat treatment, take out the package and observe whether the adhesive label blocks the air passage by its own weight, and the adhesive label arcs inward due to the shrinkage of the heat shrink layer (protective film) If the adhesive label in the arc state is re-sealed with a finger when the package is cooled to some extent, it is resealed by the adhesive strength of the adhesive layer of the adhesive label. It is impossible to stop.

<6. Function confirmation result>
In Examples 1 to 4 of the present invention, since a container having a gas barrier and a water vapor barrier, a lid, an adhesive tape, and an adhesive label were used, the functions of the gas barrier and the water vapor barrier were exhibited, and oxygen and water vapor from outside the container. It was possible to suppress the effects of changes in the content, prevent deterioration of the contents such as oxidation, and dramatically improve the storage stability of food. Further, in Examples 1 and 2, after 10 days of observation, air was injected by a syringe, the oxygen concentration in the package was reset to 5%, and then the color change of the oxygen detector was confirmed. Moreover, although Example 3 and 4 was judged from the measured value in the package after 10 days, it was confirmed that each function of the adhesive label with a function of this invention was exhibited.

  The present invention can be suitably used in the field of detecting or detecting / adjusting the environment inside the package from outside the package.

It is a top view of the ventilation path shape and adhesive label shape of this invention. It is the perspective view and sectional drawing of an example of the adhesive label of this invention. It is the side view and top view of a container (main body) used for the Example of this invention. It is the side view and top view of the lid | cover used for the Example of this invention. It is the side view and sectional drawing when the container (main body) and cover which were used for the Example of this invention were accumulated. It is a perspective view which shows an example of the package using the adhesive label of this invention, A is a case where an adhesive label is adhere | attached on a lid | cover top surface, B is a case where the adhesive label is adhere | attached on the lid | cover side surface. It is a top view which shows an example of the package using the adhesive label of this invention, and is a case where the adhesive label is adhere | attached on the lid | cover side surface of a bag.

Claims (5)

An adhesive label having a functional part is attached from the outside of a package having a ventilation path so as to cover the ventilation path, and the functional part of the adhesive label detects the environment in the package or detects the environment in the package through the ventilation path. A method for detecting or detecting / adjusting the environment inside the package to adjust the environment inside the package. The functional part of the adhesive label has at least one selected from an oxygen concentration detection agent, an oxygen absorbent, a desiccant, a humidity control agent, an ethanol transpiration agent, a carbon dioxide generating agent, a freshness maintaining agent, a temperature detection agent, and a humidity detection agent. The package internal environment detection or detection / adjustment method according to claim 1, wherein the package internal environment is detected. 3. The package environment detection or detection / adjustment according to claim 1, wherein the container, lid, packaging film, or bag forming the package contains at least one of a gas barrier resin and a water vapor barrier resin. Method. 4. The package environment detection or detection / adjustment method according to claim 1, wherein the adhesive label contains at least one of a gas barrier resin and a water vapor barrier resin. The function part of an adhesive label is covered with the protective film, The package internal environment detection or detection / adjustment method in any one of Claims 1-4 characterized by the above-mentioned.

Images