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WO2011114856A1 - Matériau de conditionnement et conditionnement utilisant celui-ci - Google Patents

Matériau de conditionnement et conditionnement utilisant celui-ci Download PDF

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Publication number
WO2011114856A1
WO2011114856A1 PCT/JP2011/054149 JP2011054149W WO2011114856A1 WO 2011114856 A1 WO2011114856 A1 WO 2011114856A1 JP 2011054149 W JP2011054149 W JP 2011054149W WO 2011114856 A1 WO2011114856 A1 WO 2011114856A1
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WO
WIPO (PCT)
Prior art keywords
film
resin
package
gas barrier
oxygen gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/054149
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English (en)
Japanese (ja)
Inventor
幹雄 田中
香代子 鬼澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kureha Corp filed Critical Kureha Corp
Priority to JP2012505587A priority Critical patent/JPWO2011114856A1/ja
Publication of WO2011114856A1 publication Critical patent/WO2011114856A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a packaging material and a packaging body using the same, and more particularly to an oxygen gas barrier packaging material and a packaging body in which an article to be packaged containing an oxidizable dye is packaged using the packaging material.
  • Fresh foods such as sashimi and processed foods such as ham have a risk of causing food poisoning due to proliferation of microorganisms if temperature control is mistaken in the distribution process or storage process.
  • anaerobic bacteria such as Clostridium botulinum may grow and cause food poisoning.
  • gas-filled packaging and gas replacement packaging that mix a small amount of oxygen (volume ratio 3 to 5%) are performed. Has the harmful effects of causing oxidative degradation of the package and promoting the growth of aerobic bacteria.
  • the present invention has been made in view of the above-described problems of the prior art, and the oxidative deterioration of the package is less likely to occur under appropriate storage conditions. It is an object of the present invention to provide a packaging material that can be easily confirmed by observing the appearance of and a package using the same.
  • the present inventors have found that the oxygen gas barrier property of the packaging material decreases when the polyglycolic acid resin used as the oxygen gas barrier material of the packaging material is hydrolyzed. And the hydrolyzability of the polyglycolic acid resin was found to depend on temperature and time. Furthermore, a package containing an easily oxidizable dye has a predetermined storage condition by utilizing the property of being oxidized and discolored when the oxygen gas barrier property of the packaging material in which it is packaged is reduced. When it deviates, it discovered that the trace could be confirmed easily by the external appearance observation of a to-be-packaged object, and came to complete this invention.
  • the packaging material of the present invention is a packaging material for packaging an article to be packaged containing an oxidizable dye, and contains a polyglycolic acid resin and a basic compound.
  • Such a packaging material preferably includes an oxygen gas barrier layer containing the polyglycolic acid resin and a layer containing the basic compound, and includes an oxygen gas barrier layer containing the polyglycolic acid resin. More preferably, the film A and the film B containing moisture are provided in a separated state, and at least one of the oxygen gas barrier layer and the film B contains the basic compound, It is further preferable that the film B includes a layer containing the basic compound.
  • the package of the present invention comprises a packaging material containing a polyglycolic acid resin and a basic compound, and an article to be packaged containing an oxidizable dye packaged with the packaging material.
  • the packaging material includes an oxygen gas barrier layer containing the polyglycolic acid resin and a layer containing the basic compound, and the packaging material is the polyglycolic acid.
  • a film A comprising an oxygen gas barrier layer containing a resin and a film B containing moisture affixed on the film A, wherein at least one of the oxygen gas barrier layer and the film B is a base
  • the packaged material is a packaging material in which the packaged material is packaged by the film A, and the film B includes a layer containing the basic compound. preferable.
  • the oxidative deterioration of the package is less likely to occur under appropriate storage conditions, and the trace can be easily confirmed by observing the appearance of the package when deviating from the predetermined storage conditions. .
  • the packaging material of the present invention is for packaging a package containing a pigment that changes color by oxidation (hereinafter, referred to as an “oxidizable pigment”), and contains a polyglycolic acid resin and a basic compound. It is preferable that it comprises a layer containing a polyglycolic acid resin and a layer containing a basic compound. .
  • Such a packaging material includes an oxygen gas barrier layer containing a polyglycolic acid resin and a basic compound (hereinafter referred to as “first packaging material”), and an oxygen gas barrier layer containing a polyglycolic acid resin.
  • first packaging material an oxygen gas barrier layer containing a polyglycolic acid resin and a basic compound
  • second packaging material an oxygen gas barrier layer containing a polyglycolic acid resin.
  • the polyglycolic acid resin (hereinafter abbreviated as “PGA resin”) has the following reaction formula:
  • the package of the present invention utilizes the fact that the oxygen gas barrier property of the film (layer) containing the PGA resin changes with temperature and time.
  • the first packaging material of the present invention uses moisture contained in the package as water used for hydrolysis, or When the package is stored and distributed under high humidity conditions, moisture in the air is used.
  • moisture content of the said film B is utilized as water used for a hydrolysis.
  • PGA-type resin is hard to be hydrolyzed with the water
  • the packaging material using the first packaging material of the present invention when a packaging material using the first packaging material of the present invention is stored and distributed under high humidity conditions, moisture in the air is supplied to the oxygen gas barrier layer in the process. Moreover, when a package containing moisture is packaged using the first packaging material of the present invention, moisture in the package is supplied to the oxygen gas barrier layer during storage. Furthermore, when storing the package body in which the package is packaged using the second packaging material of the present invention, the film B is pasted on the film A after the package body is packaged with the film A. Thereby, the moisture of the film B is supplied to the oxygen gas barrier layer.
  • the supplied water may react with the PGA resin in the oxygen gas barrier layer depending on the storage temperature and storage time to hydrolyze the PGA resin, and as a result, the oxygen gas barrier property of the oxygen gas barrier layer may be reduced. May decrease. Further, the decrease in oxygen gas barrier properties depends on the storage temperature and storage time of the package. That is, as the storage temperature of the package increases, the PGA resin is easily hydrolyzed, the oxygen gas barrier property is lowered, and the PGA resin is hydrolyzed as the storage time becomes longer at the temperature at which the PGA resin is hydrolyzed. It is easily decomposed and oxygen gas barrier properties are lowered. Furthermore, such a hydrolysis rate is accelerated by the basic compound, and the oxygen gas barrier property is remarkably lowered.
  • the package to be packaged by the packaging material of the present invention contains an easily oxidizable dye, and as described above, the packaging material is discolored due to oxidation when the oxygen gas barrier property of the packaging material is lowered. This makes it possible to easily check the temperature history of the package during storage.
  • polyglycolic acid resin There is no restriction
  • a glycolic acid homopolymer consisting only of glycolic acid repeating units represented by the formula (hereinafter referred to as “PGA homopolymer”, including a ring-opened polymer of glycolide which is a bimolecular cyclic ester of glycolic acid). And a polyglycolic acid copolymer containing glycolic acid repeating units (hereinafter referred to as “PGA copolymer”).
  • the content of the glycolic acid repeating unit in the PGA copolymer is preferably 60% by mass or more.
  • the content of the glycolic acid repeating unit is less than the lower limit, the crystallinity of the PGA copolymer is lowered, and the oxygen gas barrier property and heat resistance of the resulting packaging material tend to be lowered.
  • repeating unit other than the glycolic acid repeating unit in such a PGA copolymer examples include the following formulas (2) to (6):
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and k represents an integer of 2 to 10.
  • the melting point of the PGA-based resin can be lowered.
  • the processing temperature can be lowered, and the melting Thermal decomposition during processing can be reduced.
  • the upper limit of the content of the repeating unit represented by the above formulas (2) to (6) is preferably 40% by mass or less.
  • the PGA homopolymer used in the present invention can be synthesized by dehydration polycondensation of glycolic acid, dealcoholization polycondensation of glycolic acid alkyl ester, ring-opening polymerization of glycolide, and the like.
  • it is synthesized by ring-opening polymerization carried out by heating to a temperature of about 120 to 250 ° C. in the presence of a polymerization catalyst such as a tin compound, a titanium compound, an aluminum compound, a zirconium compound or an antimony compound. Is preferred.
  • a polymerization catalyst such as a tin compound, a titanium compound, an aluminum compound, a zirconium compound or an antimony compound. Is preferred.
  • Such ring-opening polymerization can be carried out by either bulk polymerization or solution polymerization.
  • the PGA copolymer can be synthesized by using a comonomer in combination in the polycondensation reaction or the ring-opening polymerization reaction.
  • comonomers include ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactides, lactones (eg, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -pivalolactone, ⁇ - Butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.), carbonates (eg, trimethylene carbonate, etc.), ethers (eg, 1,3-dioxane, etc.), ether esters ( For example, cyclic monomers such as dioxanone), amides (such as ⁇ -caprolactam); hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybuta
  • comonomers may be used individually by 1 type, or may use 2 or more types together.
  • a cyclic monomer and a hydroxycarboxylic acid are preferred from the viewpoint that a PGA copolymer that is easy to copolymerize and has excellent physical properties can be obtained.
  • Such PGA-type resin may be used individually by 1 type, or may use 2 or more types together.
  • the melt viscosity (temperature 270 ° C., shear rate 120 sec ⁇ 1 ) of the PGA resin used in the present invention is preferably 300 to 10,000 Pa ⁇ s, more preferably 400 to 8,000 Pa ⁇ s, and more preferably 500 to 5 1,000 Pa ⁇ s is particularly preferable.
  • the melting point of the PGA resin is preferably 200 ° C. or higher, and more preferably 210 ° C. or higher.
  • PGA-based resin may be used alone, but within a range not impairing the object of the present invention, an inorganic filler, other thermoplastic resin, plasticizer, etc. are added to the PGA-based resin. You may use as a mix
  • PGA-based resins and PGA-based resin compositions include heat stabilizers, light stabilizers, moisture-proofing agents, waterproofing agents, water repellents, lubricants, mold release agents, coupling agents, oxygen absorbers as necessary.
  • Various additives such as pigments and dyes can be contained.
  • the packaging material of the present invention contains a basic compound.
  • This basic compound has an action of promoting the hydrolysis reaction of the PGA-based resin described above, and this action also promotes a reduction in oxygen gas barrier properties of the oxygen gas barrier layer. As a result, oxygen gas easily penetrates into the package, and the oxidizable dye in the package becomes more oxidized and its discoloration becomes prominent, so it is easy to visually check the traces that deviate from the specified storage conditions. It becomes possible to do.
  • the basic compound used in the present invention is not particularly limited as long as it can accelerate the hydrolysis reaction of the PGA resin.
  • amines such as ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.
  • the hydroxide is mentioned.
  • the content of the basic compound in the packaging material of the present invention is an amount that can promote the hydrolysis reaction of the PGA-based resin and that the discoloration of the package can be sufficiently visually recognized due to the decrease in the oxygen gas barrier property of the oxygen gas barrier layer.
  • the appropriate content of the basic compound varies depending on the type of the basic compound, the temperature history range monitored by the packaging material of the present invention, and it is difficult to specify precisely.
  • the amount is preferably 1.0 ⁇ 10 ⁇ 6 to 2.0 mol / cm 3 per cm 3 of the oxygen gas barrier layer.
  • the content of the basic compound is less than the lower limit, the hydrolysis reaction is hardly promoted, and the effect of adding the basic compound tends to be insufficient.
  • the content exceeds the upper limit the PGA-based resin can be obtained in a short time. The hydrolysis reaction is promoted, and even under appropriate storage conditions, the oxygen gas barrier property is lowered and the packaged material may be discolored.
  • the first packaging material of the present invention is a package containing an oxidizable dye and water, or contains an oxidizable dye and is stored and distributed under high humidity conditions (preferably a relative humidity of 90% RH or more). It is for wrapping an object to be packaged (which may contain water), and includes an oxygen gas barrier layer containing the PGA-based resin and the basic compound.
  • an oxygen gas barrier layer may be composed of one layer containing a PGA resin and a basic compound, or a layer containing a PGA resin (hereinafter referred to as “PGA resin layer”). It may be composed of two layers including a layer containing a basic compound (hereinafter referred to as “basic compound layer”).
  • the first packaging material of the present invention as a method for producing a single layer oxygen gas barrier layer containing a PGA resin and a basic compound, (i) a composition containing a PGA resin and a basic compound And a method of forming the composition into a film by a known method for producing a PGA-based resin film and stretching it as necessary; (ii) producing a PGA-based resin film by a known method; A method of impregnating a compound and stretching it as necessary; (iii) A method of making a PGA resin stretched film by a known method and then impregnating the film with a basic compound; (iv) A method of producing by a known method A method in which a basic compound (preferably a volatile basic compound) is sprayed and permeated into a PGA-based resin film or a stretched PGA-based resin film; (v) by a known method Examples thereof include a method in which the prepared PGA-based resin film or PGA-based resin stretched film is exposed to a basic compound
  • the PGA resin film (or PGA resin stretched film) is produced, the PGA resin film (or the There is an advantage that a basic compound can be permeated into the PGA-based resin stretched film).
  • the thickness of such a single-layer oxygen gas barrier layer is preferably 1 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • the thickness of the oxygen gas barrier layer is less than the lower limit, sufficient gas barrier properties tend not to be obtained, and film thickness control during extrusion and film formation tends to be difficult.
  • the thickness of the oxygen gas barrier layer exceeds the above upper limit, the rigidity of the packaging body increases excessively, and there is a tendency to suffer an economic disadvantage that the amount of packaging material discarded increases.
  • an oxygen gas barrier layer comprising two layers of a PGA-based resin layer and a basic compound layer
  • a PGA-based resin film produced by a known method or a PGA-based resin stretched film and a basic compound-containing layer (Ii) A method of coating a basic compound on a PGA resin film or a stretched PGA resin film produced by a known method; (iii) A PGA resin produced by a known method and others A method in which a basic compound (preferably a volatile basic compound) is sprayed on a laminated film of the resin and the basic compound is permeated into at least another resin layer; (iv) a PGA resin prepared by a known method; A laminated film with other resin is exposed to a gas atmosphere of a basic compound (preferably a volatile basic compound) to form a salt on at least the other resin layer.
  • a basic compound preferably a volatile basic compound
  • a method of infiltrating the basic compound may be used.
  • a resin film containing a basic compound can be used.
  • Examples of the method of applying the basic compound in the method (ii) include coating and printing.
  • the thickness of the PGA resin layer is preferably 1 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • the thickness of the PGA-based resin layer is less than the lower limit, sufficient gas barrier properties tend not to be obtained, and film thickness control during extrusion and film formation tends to be difficult.
  • the thickness of the PGA-based resin layer exceeds the upper limit, the rigidity of the packaging body is excessively increased, and there is a tendency to suffer an economic disadvantage that the amount of packaging material discarded increases.
  • the thickness of the basic compound layer is preferably 1 to 1000 ⁇ m, more preferably 1 to 500 ⁇ m.
  • the thickness of the basic compound layer is less than the lower limit, the content of the basic compound is decreased, and the hydrolysis reaction of the PGA resin tends not to be sufficiently promoted.
  • the upper limit is exceeded, the packaging material is discarded. There is a tendency to suffer the economic disadvantage of increasing volume.
  • such an oxygen gas barrier layer containing a PGA-based resin and a basic compound may be formed over the entire surface direction of the packaging material, but is excellent in appropriate storage conditions. In view of the fact that it exhibits oxygen gas barrier properties, and if it deviates from that, the wrapping is partially discolored so that oxidative deterioration of the wrapping can be more easily visually recognized. It is preferable that an oxygen gas barrier layer containing a PGA resin and a basic compound is formed, and an oxygen gas barrier layer made of a PGA resin not containing a basic compound is formed in the remaining portion.
  • the first packaging material of the present invention it is preferable to provide an inner layer on one surface of the oxygen gas barrier layer in order to avoid contact between the oxygen gas barrier layer and the package.
  • an inner layer in the case where the first package of the present invention uses moisture contained in the package, it has moisture permeability (water vapor permeability) and is made of PGA resin. It is necessary that the effect of the hydrolysis on the deterioration of the oxygen gas barrier property of the first packaging material is small.
  • the resin constituting the inner layer satisfying such conditions include polyethylene resin, polypropylene resin, ionomer resin, ethylene-vinyl acetate copolymer resin, polyamide resin, polyethylene terephthalate resin, and polylactic acid resin.
  • polyolefin resin such as polyethylene resin is relatively difficult to pass moisture, it is preferably used as a thin film or a film perforated by a known method.
  • the inner layer may be formed by coextrusion molding together with the oxygen gas barrier layer, or may be formed by laminating an inner layer film on the oxygen gas barrier layer.
  • the oxygen gas barrier layer and the inner layer film may be bonded using an adhesive resin.
  • such an inner layer may be a single layer or a multilayer of two or more layers.
  • the thickness of such an inner layer is preferably 5 to 50 ⁇ m, more preferably 5 to 40 ⁇ m.
  • the thickness of the inner layer is less than the lower limit, the strength of the package is insufficient, and there is a tendency that sufficient sealing strength cannot be obtained when sealing, and when the upper limit is exceeded, the moisture of the packaged product becomes an oxygen gas barrier.
  • the PGA-based resin in the oxygen gas barrier layer is not hydrolyzed even if the storage temperature of the package deviates from a predetermined condition without being sufficiently supplied to the layer.
  • the thickness of the inner layer can be increased.
  • the thickness of such an inner layer is preferably 5 to 150 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the thickness of the inner layer is less than the lower limit, the strength of the package is insufficient, and there is a tendency that sufficient sealing strength cannot be obtained when sealing, and when the upper limit is exceeded, the rigidity of the packaging material becomes too large. In addition, there is a tendency to suffer an economic disadvantage of increasing the amount of packaging materials discarded.
  • an outer layer may be provided on one surface of the oxygen gas barrier layer in order to increase the strength of the packaging material.
  • outer layers include polyamide resin layers, polyester resin layers, polycarbonate resin layers, polystyrene resin layers, polyolefin resin layers, cyclic olefin resin layers, polyurethane resin layers, ionomer resin layers, and polylactic acid.
  • thermoplastic resin layers such as resin-based resin layers. Among them, polyamide-based resin layers, polyester-based resin layers, polyolefin-based resin layers, and polylactic acid-based resin layers from the viewpoints of transparency, surface hardness, printability, and heat resistance. Is preferred.
  • the outer layer may be formed by coextrusion with the oxygen gas barrier layer, or may be formed by laminating an outer layer film on the oxygen gas barrier layer. Moreover, you may adhere
  • the thickness of such an outer layer is preferably 1 to 30 ⁇ m, and more preferably 1 to 20 ⁇ m.
  • the thickness of the outer layer is less than the lower limit, the strength of the package tends to be insufficient.
  • the thickness exceeds the upper limit a decrease in oxygen gas barrier property due to hydrolysis of the PGA-based resin may occur. It becomes difficult to be reflected in the discoloration due to oxidation of, and the hardness of the packaging material tends to increase too much.
  • the second packaging material of the present invention comprises a film A having an oxygen gas barrier layer containing a PGA-based resin and a film B containing moisture in a separated state, and the oxygen gas barrier layer and the film B At least one of them contains a basic compound.
  • the thickness of the oxygen gas barrier layer is preferably 1 to 20 ⁇ m, and preferably 1 to 10 ⁇ m. Is more preferable.
  • the thickness of the oxygen gas barrier layer is less than the lower limit, sufficient gas barrier properties tend not to be obtained, and film thickness control during extrusion and film formation tends to be difficult.
  • the thickness of the oxygen gas barrier layer exceeds the above upper limit, the rigidity of the packaging body increases excessively, and there is a tendency to suffer an economic disadvantage that the amount of packaging material discarded increases.
  • the manufacturing method of a well-known PGA-type resin film is mentioned as a manufacturing method of such an oxygen gas barrier layer.
  • Such an oxygen gas barrier layer containing a PGA-based resin is preferably formed over the entire surface direction of the film A.
  • the oxygen gas barrier layer may be composed of one layer containing a PGA-based resin and a basic compound. It may consist of two layers of a layer containing a resin (hereinafter referred to as “PGA resin layer”) and a layer containing a basic compound (hereinafter referred to as “basic compound layer”).
  • PGA resin layer a layer containing a resin
  • basic compound layer a layer containing a basic compound
  • the thickness of the oxygen gas barrier layer composed of one layer containing such a PGA-based resin and a basic compound the effect thereof, and the production method thereof
  • the case of the oxygen gas barrier layer composed of one layer in the first packaging material The method for producing an oxygen gas barrier layer comprising two layers of a PGA-based resin layer and a basic compound layer, and the thicknesses and effects of the PGA-based resin layer and the basic compound layer are described above. This is the same as the case of the oxygen gas barrier layer consisting of two layers in the first packaging material.
  • Such an oxygen gas barrier layer containing a PGA-based resin and a basic compound may be formed over the entire surface direction of the film A, but exhibits an excellent oxygen gas barrier property under appropriate storage conditions.
  • a PGA-based resin and a basic compound in a part of the surface direction of the film A It is preferable that an oxygen gas barrier layer containing a PGA-based resin not containing a basic compound is formed in the remaining portion.
  • the film A it is preferable to provide an inner layer on one surface of the oxygen gas barrier layer in order to avoid contact between the oxygen gas barrier layer and an article to be packaged.
  • the resin layer illustrated as an outer layer in said 1st packaging material is mentioned.
  • the thickness of the inner layer is preferably 5 to 150 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the thickness of the inner layer is less than the lower limit, the strength of the package is insufficient, and there is a tendency that sufficient sealing strength cannot be obtained when sealing, and when the upper limit is exceeded, the rigidity of the packaging material becomes too large.
  • the method for producing such an inner layer include the same method as that for the inner layer in the first packaging material.
  • an outer layer may be provided on one surface of the oxygen gas barrier layer in order to increase the strength of the packaging material.
  • the 2nd package of this invention utilizes the water
  • the outer layer having such moisture permeability include the resin layer exemplified as the inner layer in the first packaging material.
  • the thickness of the outer layer is preferably 1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m. When the thickness of the outer layer is less than the lower limit, the strength of the package tends to be insufficient. On the other hand, when the upper limit is exceeded, the moisture permeability decreases and the hardness of the packaging material increases or the transparency decreases. There is a tendency.
  • the same method as the case of the outer layer in said 1st packaging material is mentioned.
  • the film B constituting the second packaging material of the present invention contains moisture, and examples thereof include a substrate film impregnated with moisture.
  • the film B is stored in a state separated from the film A before use (before packaging), and the outer surface (specifically, oxygen) of the film A at the time of use (immediately before use or after packaging). Affixed on the gas barrier layer).
  • the water in the film B is supplied to the oxygen gas barrier layer of the film A, and the PGA resin can be hydrolyzed.
  • this film B may consist of two layers, the layer containing a water
  • a single layer containing water and a basic compound is preferable.
  • the material containing polysaccharides such as a cellulose, a cellophane, a polyvinyl alcohol type
  • group examples thereof include resins, urea resins, polyacrylates and the like.
  • the thickness of such a substrate film is not particularly limited, but is preferably 1 to 2000 ⁇ m.
  • the water content in the film B is not particularly limited as long as the hydrolysis reaction of the PGA resin can be promoted and the oxygen gas barrier property can be lowered when deviating from predetermined storage conditions.
  • the appropriate water content in the film B varies depending on the material of the film B and the method of attaching to the film A, and thus it is difficult to strictly define, for example, 100 per cm 3 of the film B. ⁇ 5000 mg / cm 3 is preferred.
  • the moisture content is less than the lower limit, the amount of moisture supplied to the oxygen gas barrier layer of the film A is small, and even when the moisture content deviates from the predetermined storage conditions, hydrolysis of the PGA resin hardly occurs.
  • the upper limit is exceeded, excessive moisture leaks from the film B, resulting in poor appearance of the package, or the film B is easily peeled off from the film A. Tend to be.
  • the method for attaching the film B according to the present invention is not particularly limited as long as the method can fix the film B to the outer surface of the film A.
  • the film B may be covered with an adhesive-attached film and fixed to the outer surface of the film A, or an adhesive layer may be provided on a part of the surface of the film B that is attached to the film A.
  • the film B imparted with properties may be directly bonded and fixed to the outer surface of the film A.
  • the adhesive that constitutes the adhesive layer of the film B or the adhesive-attached film.
  • acrylic resin, olefin resin, urethane resin, ethylene-vinyl acetate resin, epoxy resin examples of the adhesive include silicone resin.
  • the said film with an adhesive agent is colorless and transparent so that the discoloration of a to-be-packaged object can be visually recognized.
  • a layer (hereinafter referred to as “moisture dissipation prevention”) is provided on the surface opposite to the surface to which the film B is applied so that the water supply to the film A is not hindered. It is preferable to provide a layer. Further, instead of providing such a moisture dissipation prevention layer on the film B in advance, after the film B is attached to the outer surface of the film A, a film having a moisture dissipation prevention layer may be attached on the film B. Alternatively, a film having a moisture dissipation prevention layer and an adhesive layer may be used as the adhesive-attached film.
  • the moisture dissipation prevention layer is preferably colorless and transparent so that discoloration of the package can be visually recognized.
  • the resin constituting such a moisture dissipation prevention layer there are no particular restrictions on the resin constituting such a moisture dissipation prevention layer.
  • the resin constituting such a moisture dissipation prevention layer.
  • polyethylene resin polypropylene resin, ethylene-vinyl acetate copolymer resin, polyamide resin, polyethylene terephthalate resin, polycarbonate resin, polylactic acid resin Etc.
  • the packaging material of the present invention is a packaging material for packaging an object to be packaged containing an easily oxidizable pigment.
  • the oxidizable dye include heme dye and derivatives thereof (eg, myoglobin, hemoglobin, nitrosyl myoglobin), chlorophyll and derivatives thereof, carotenoids (eg, ⁇ -carotene, lycopene, cryptoxanthine, astaxanthin), anthocyanins, flavonoids And the like.
  • natural colorants such as anato dye, turmeric dye, krill dye, gardenia dye, cucumber dye, red cabbage dye, cochineal dye, red pepper dye, tomato dye, red pepper dye, safflower dye, purple potato dye, and lac dye.
  • Examples of the package containing such an easily oxidizable pigment include, for example, livestock meat (for example, beef, pork, poultry, lamb, salmon), seafood (for example, tuna, bonito, yellowtail, amberjack, Horse mackerel, Vietnamese, other bloody meat, crustacean such as shrimp and crab), vegetables, fruits, salmon, seaweed, and their cooked products (eg seasoned meat, sushi, grilled fish, ham, sausage) , Kamaboko, salad, side dish, juice, soup), raw juices, dairy products (cheese, butter), and pharmaceuticals colored with natural pigments.
  • livestock meat for example, beef, pork, poultry, lamb, salmon
  • seafood for example, tuna, bonito, yellowtail, amberjack, Horse mackerel, Thai, other bloody meat, crustacean such as shrimp and crab
  • vegetables fruits, salmon, seaweed
  • cooked products eg seasoned meat, sushi, grilled fish, ham, sausage
  • Kamaboko salad, side dish, juice, soup
  • raw juices dairy
  • the package is not particularly limited as long as it contains moisture, but moisture penetrates the inner layer.
  • the water activity (Aw) of the packaged object is preferably 0.90 to 1.00, more preferably 0.95 to 1.00. preferable.
  • packages containing such oxidizable pigments and moisture include livestock meat (eg, beef, pork, poultry, lamb, salmon), fish (eg, tuna, skipjack, yellowtail, amberjack, horse mackerel, Thailand, other bloody meat, shellfish such as shrimp and crab), vegetables, fruits, potatoes, seaweeds, and their cooked products (eg seasoned meat, sushi, grilled fish, ham, sausage, kamaboko , Salads, prepared dishes, soups, etc.), raw juices, foods such as dairy products (cheese, butter), and liquid pharmaceuticals colored with natural pigments.
  • livestock meat eg, beef, pork, poultry, lamb, salmon
  • fish eg, tuna, skipjack, yellowtail, amberjack, horse mackerel, Thailand, other bloody meat, shellfish such as shrimp and crab
  • vegetables eg seasoned meat, sushi, grilled fish, ham, sausage, kamaboko , Salads, prepared dishes, soups, etc.
  • raw juices eg., foods
  • the package of the present invention comprises a packaging material containing a PGA-based resin and a basic compound, and an article to be packaged containing an easily oxidizable pigment packaged by the packaging material.
  • the packaging material comprising the first packaging material of the present invention and the packaging material containing the easily oxidizable dye and moisture, or containing the easily oxidizable dye. And stored and distributed under high humidity conditions (relative humidity of 90% RH or higher) (hereinafter collectively referred to as “first package”); What is provided with the to-be packaged object containing the oxidizable pigment
  • a first package of the present invention includes a packaging material including an oxygen gas barrier layer containing a PGA-based resin and a basic compound, and an article to be packaged containing an oxidizable dye and moisture, Alternatively, it includes an easily oxidizable dye and a packaged article that is stored and distributed under high humidity conditions (relative humidity of 90% RH or more).
  • a package containing water in the first package of the present invention, includes an inner layer, the oxygen gas barrier layer disposed on the inner layer, and an outer layer disposed on the oxygen gas barrier layer.
  • packaging with packaging material in order to supply moisture in the packaged material to the oxygen gas barrier layer of the packaging material, package the packaged product with a moisture-permeable layer as the inner layer (layer on the packaged product side)
  • a layer having moisture permeability is used to supply moisture in a high humidity environment to the oxygen gas barrier layer of the packaging material.
  • the inner layer does not have to be moisture permeable.
  • a film A having an oxygen gas barrier layer containing a PGA-based resin, an article to be packaged containing an easily oxidizable dye packaged by the film A, and the film A Attached film B containing water and a basic compound (hereinafter referred to as “second package A”);
  • the film A comprising an oxygen gas barrier layer containing a PGA-based resin and a basic compound And an article to be packaged containing the easily oxidizable pigment packaged by the film A, and a film B containing moisture affixed on the film A (hereinafter referred to as “second package B”).
  • the basic compound may be contained in both the oxygen gas barrier layer and the film B.
  • the oxygen gas barrier layer containing the PGA resin is preferably formed over the entire surface direction of the film A.
  • the package is less susceptible to oxidative degradation and can be stored for a long period of time, and the film B can be attached to any position of the film A, easily. It can be handled.
  • the film B may be applied to the entire surface direction of the film A, but the packaged material partially discolors when deviating from appropriate storage conditions. From the viewpoint that the oxidative degradation of the package can be more easily visually recognized, it is preferable that the film A is attached to a part in the surface direction.
  • the oxygen gas barrier layer containing the PGA-based resin and the basic compound may be formed over the entire surface direction of the film A, but under appropriate storage conditions. From the viewpoint of exhibiting excellent oxygen gas barrier properties and, when deviating from that, the wrapping is partially discolored, so that the oxidative deterioration of the wrapping can be more easily recognized. It is preferable that an oxygen gas barrier layer made of a PGA resin not containing a basic compound is formed in the remaining portion. Further, in the second package B, from the viewpoint that the oxidative degradation of the package can be more easily visually recognized because the package is partially discolored when deviating from an appropriate storage condition, an oxygen gas barrier is provided.
  • the film B is preferably attached to a part of the surface direction of the film A, and the oxygen gas barrier layer is one of the surface directions of the film A.
  • the film B is preferably pasted on the oxygen gas barrier layer.
  • the moisture in the film B (in the case of the second package A, further basic compound) is The oxygen gas barrier layer is supplied, and the PGA resin of the oxygen gas barrier layer can be hydrolyzed. And when the storage condition of the package in such a state deviates from a predetermined condition, the hydrolysis reaction of the PGA resin proceeds and the oxygen gas barrier property is lowered. As a result, external oxygen penetrates into the package and the oxidizable dye in the package is oxidized and discolored.By visually observing the appearance of the package, the package is subjected to predetermined storage conditions. The trace which deviated from can be confirmed easily.
  • the film A a packaging material including an inner layer, the oxygen gas barrier layer disposed on the inner layer, and an outer layer disposed on the oxygen gas barrier layer is used.
  • a packaging material including an inner layer, the oxygen gas barrier layer disposed on the inner layer, and an outer layer disposed on the oxygen gas barrier layer is used.
  • Example 1 As the resin for each layer, polyethylene terephthalate resin pellets (“Bellpet IFG-8L” manufactured by Bell Polyester Products Inc .; hereinafter abbreviated as “PET resin”) and nylon resin pellets (“Amilan CM6241FS” manufactured by Toray Industries, Inc.).
  • PET resin polyethylene terephthalate resin pellets
  • nylon resin pellets Similar CM6241FS manufactured by Toray Industries, Inc.
  • Ny6-66 resin PGA homopolymer pellets (manufactured by Kureha Corporation, melt viscosity (temperature 270 ° C., shear rate 120 sec ⁇ 1 ): 1600 Pa ⁇ s, melting point: 224 ° C.), And a linear low-density polyethylene resin (“moretec 0238CN” manufactured by Idemitsu Petrochemical Co., Ltd., hereinafter abbreviated as “LLDPE resin”), and a polyolefin-based adhesive (Mitsubishi Chemical Corporation) as an adhesive between each layer.
  • LLDPE resin linear low-density polyethylene resin
  • LLDPE resin polyolefin-based adhesive
  • PET resin (thickness: 2 ⁇ m) // Ny6-66 by coextrusion molding using “Modic F563” manufactured by A multilayer film (film A according to the present invention) made of resin (thickness: 8 ⁇ m) // PGA resin (thickness: 3 ⁇ m) // LLDPE resin (thickness: 21 ⁇ m) was produced.
  • oxygen gas permeability at 15 ° C. and 80% RH of this multilayer film was measured according to JIS K7126 (Method B), it was 3.0 cm 3 / (m 2 ⁇ day ⁇ atm).
  • filter paper manufactured by Advantech Toyo Co., Ltd., thickness: 170 ⁇ m
  • aqueous ammonia 2.3 ⁇ 10 ⁇ 3 mol of ammonia per 1 cm 3 of film B) / Cm 3
  • a three-sided seal is applied using the LLDPE resin layer of the multilayer film (film A) as an inner layer to produce a pouch (inner dimensions: 8 cm ⁇ 8 cm), which contains myoglobin (an oxidizable dye) as an article to be packaged
  • the beef minced meat 30g was enclosed and vacuum-packed.
  • moisture content and ammonia was mounted on the PET resin layer surface of the pouch which vacuum-packed the beef minced meat, and the packing tape made from polypropylene resin (Sekisui Chemical Co., Ltd. 4cm x 4 cm) and bonded and fixed to produce a package of the present invention.
  • FIG. 1A shows the state of the package in each storage time (from the top, day 0, day 3, day 7).
  • the photograph on the left side of FIG. 1B shows the state of the beef minced meat taken out by opening the package stored for 7 days.
  • no discoloration of beef minced meat was observed even when stored at 10 ° C. for 3 days.
  • the beef minced meat turned greenish brown and was visually confirmed to be inedible.
  • the three panelists judged the smell of beef minced meat taken out by opening the package stored for 7 days according to the following criteria.
  • the number of viable bacteria per 1 g of beef minced meat stored for 7 days was measured by a pour plate method (cultured at 37 ° C. for 48 hours) using a standard agar medium, and it was 4.9 ⁇ 10 7 cfu / g. there were. From this result, the beef minced meat stored at 10 ° C. for 7 days reached the initial rotting level (10 7 cfu / g or more), and was confirmed to be inedible. Moreover, although the result of the said visual observation corresponds with this viable cell count measurement result, it turned out that the result of odor determination does not correspond.
  • VLDPE resin As a resin for each layer, an ultra-low density polyethylene resin (“moretech V0398CN” manufactured by Prime Polymer Co., Ltd., hereinafter abbreviated as “VLDPE resin”), an ionomer resin (“High Milan AM79301” manufactured by Mitsui DuPont Polychemical Co., Ltd.).
  • VLDPE resin ultra-low density polyethylene resin
  • ionomer resin High Milan AM79301 manufactured by Mitsui DuPont Polychemical Co., Ltd.
  • VLDPE resin Polyvinylidene chloride
  • EVAFLEX V5714C ethylene-vinyl acetate copolymer resin
  • EVA resin EVA resin by coextrusion molding using “EVA resin”
  • a multilayer film composed of (thickness: 24 ⁇ m) was produced. The oxygen gas permeability of this multilayer film at 15 ° C.
  • Example 2 A package was produced in the same manner as in Example 1 except that this multilayer film was used as film A and an EVA resin layer was used as an inner layer to produce a pouch (inner dimensions: 8 cm ⁇ 8 cm).
  • FIG. 1A shows the state of the package in each storage time (from the top, 0th day, 3rd day, 7th day).
  • FIG. 1B shows the state of the beef minced meat taken out by opening the package stored for 7 days.
  • Example 2 Cellophane (manufactured by Toyo Corp., thickness: 18 ⁇ m) was cut into 2 cm ⁇ 2 cm, and 10 ⁇ l of 2.8% by mass of aqueous ammonia (2.2 ⁇ 10 ⁇ 3 mol / cm 3 of ammonia per 1 cm 3 of film B) The film containing water and ammonia was produced. A package was produced in the same manner as in Example 1 except that this film was used as the film B.
  • FIG. 2A shows the state of the package in each storage time (from the top, 0th day, 3rd day, 7th day).
  • FIG. 2B shows the state of the beef minced meat that has been unpacked after being unpacked for 7 days.
  • no discoloration of beef minced meat was observed even when stored at 10 ° C. for 3 days.
  • the part where the film B was applied and its peripheral part The beef minced meat turned greenish brown and visually confirmed to be inedible.
  • Comparative Example 2 In the same manner as in Example 2, a film containing water and ammonia (base material: cellophane) was produced. A package was produced in the same manner as in Comparative Example 1 except that this film was used as the film B.
  • FIG. 2A shows the state of the package in each storage time (from the top, 0th day, 3rd day, 7th day).
  • the photograph on the right side of FIG. 2B shows the state of the beef minced meat taken out by opening the package stored for 7 days.
  • Example 3 Cellophane (manufactured by Toyo Corporation, thickness: 18 ⁇ m) was cut into 2 cm ⁇ 2 cm, and 10 ⁇ l of 0.28% by mass of aqueous ammonia (2.2 ⁇ 10 ⁇ 4 mol / cm 3 of ammonia per 1 cm 3 of film B) The film containing water and ammonia was produced. A package was produced in the same manner as in Example 1 except that this film was used as the film B.
  • the package was stored at 5 ° C, 15 ° C, and 25 ° C in the dark.
  • the photographs in Fig. 3 show the packaging at each storage temperature (5 ° C, 15 ° C, 25 ° C from the top) and each storage time (4th, 7th, 9th from the left set). It shows the state of the body. Table 1 shows the results of visual observation of these.
  • the packaging body of each storage temperature and each storage time was opened, beef minced meat was taken out, and the odor was judged by three panelists in the same manner as in Example 1. The results are shown in Table 1. Further, the number of viable bacteria per 1 g of beef minced meat at each storage temperature and each storage time was measured in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 3 In the same manner as in Example 3, a film containing water and ammonia (base material: cellophane) was produced. A package was produced in the same manner as in Comparative Example 1 except that this film was used as the film B.
  • the package was stored at 5 ° C, 15 ° C, and 25 ° C in the dark.
  • the photographs in Fig. 3 show the packaging at each storage temperature (from the top 5 °C, 15 °C, 25 °C) and each storage time (4th, 7th, 9th from the left set). It shows the state of the body.
  • Table 2 shows the results of visual observation of these.
  • the packaging body of each storage temperature and each storage time was opened, beef minced meat was taken out, and the odor was judged by three panelists in the same manner as in Example 1. The results are shown in Table 2. Further, the number of viable bacteria per 1 g of beef minced meat at each storage temperature and each storage time was measured in the same manner as in Example 1. The results are shown in Table 2.
  • the number of viable bacteria per gram of beef minced meat is shown to be an initial corrosion level (10 7 cfu unsuitable for food use even at storage for 9 days at a storage temperature of 5 ° C. / G or more), but reached the 7th day at 15 ° C and the 4th day at 25 ° C. From this, it was found that when the storage temperature was 5 ° C., both the results of the visual observation and the odor determination were in agreement with the viable cell count measurement results. On the other hand, at 15 ° C. and 25 ° C., it was found that the results of the visual observation and the odor determination did not coincide with the viable cell count measurement results.
  • the oxidative deterioration of the package is less likely to occur under an appropriate storage condition, and the trace is easily confirmed by observing the appearance of the package when deviating from the predetermined storage condition. It is possible to prevent accidental eating of foods that have reached the level of spoilage.
  • the packaging material of the present invention is suitable for packaging of an article to be discolored due to oxidative degradation, livestock meat, fish meat, vegetables, fruits, potatoes, seaweeds, cooked products thereof, and raw juices It is useful as a packaging material for packaging foods such as dairy products and pharmaceuticals colored with natural pigments.

Landscapes

  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Packages (AREA)

Abstract

L'invention concerne un conditionnement comportant un matériau de conditionnement, qui contient une résine à base d'acide polyglycolique et un composé de base, et un article, qui contient un pigment facilement oxydable, ledit article étant conditionné dans ledit matériau de conditionnement.
PCT/JP2011/054149 2010-03-17 2011-02-24 Matériau de conditionnement et conditionnement utilisant celui-ci Ceased WO2011114856A1 (fr)

Priority Applications (1)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006104114A1 (fr) * 2005-03-28 2006-10-05 Kureha Corporation Feuille stratifiee a base de resine d’acide polyglycolique et sa methode de fabrication
JP2008221811A (ja) * 2007-03-16 2008-09-25 Dainippon Printing Co Ltd バリア性を有するヒ−トシ−ル性フィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006104114A1 (fr) * 2005-03-28 2006-10-05 Kureha Corporation Feuille stratifiee a base de resine d’acide polyglycolique et sa methode de fabrication
JP2008221811A (ja) * 2007-03-16 2008-09-25 Dainippon Printing Co Ltd バリア性を有するヒ−トシ−ル性フィルム

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