JP2006131242A - Oxygen-absorptive packaging mounting member and package mounted with it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen-absorptive packaging mounting member or the like capable of efficiently removing dissolved oxygen in a product by bringing the oxygen-absorptive packaging mounting member into direct contact with the content in a liquid, and having no possibility of generating cracks in a compounded resin layer caused by expansion of the volume, leaking of the content and generating a foreign taste. <P>SOLUTION: The oxygen-absorptive packaging mounting member characterized by that the whole packaging mounting member or at least a part of it comprises a resin composition compounded with an oxygen absorbing agent is provided in the packaging mounting member in which the content can be taken out by mounting it on a package. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a packaging mounting member that is exposed both inside and outside of a packaging body such as a plug, spout and dispenser, comprising a resin composition containing an oxygen absorbent and a thermoplastic resin, and the packaging thereof. The present invention relates to a package equipped with a mounting member.

  More specifically, the packaging mounting member directly contacts the liquid contents, thereby accelerating the absorption rate of dissolved oxygen, preventing deterioration of the contents due to residual oxygen, and providing a package that can be stored for a long period of time. Is.

  Not only food related products such as fruit juice, liquor, wine, tea, but also non-food related products such as liquid detergents, shampoos, dyes, etc., oxygen in the headspace of the package and dissolved oxygen in the product are effective for the product. Altering ingredients, changing quality such as flavor and color tone, significantly lowering the commercial value. Conventionally, such products that are easily oxidized are filled in oxygen-barrier packaging using aluminum foil or the like, or sealed with vacuum packaging or gas replacement, such as ascorbic acid, gallic acid, reduced iron, etc. We have responded with packaging technology such as coexisting more easily oxidizable substances as oxygen scavengers. However, in such a case, a manufacturing process for removing oxygen is added, which causes a problem that the manufacturing cost increases.

  Recently, attempts have been made to prevent deterioration of the contents by providing the package itself with a function of absorbing oxygen. However, even in this case, since the reaction rate with oxygen is slow, there is a problem that an effective effect on the contents is not exhibited. In particular, when the contents are liquid, the absorption rate of dissolved oxygen in the product tends to be slower than the oxygen absorption in the head space, and there has been a demand for increasing the oxygen absorption rate.

The present invention has been made in view of the drawbacks of the related art, and in a package provided with an oxygen barrier layer, by mounting a package mounting member made of a resin composition containing an oxygen absorbent, an appropriate speed can be achieved. In this way, oxygen is absorbed. Recently, an oxygen absorbent containing an inorganic compound having oxygen defects, particularly titanium dioxide as an active ingredient has been proposed. (Patent Document 1)
The present invention accelerates the absorption rate of dissolved oxygen by directly contacting the liquid contents with a packaging mounting member containing such an oxygen absorbent, and prevents the contents from being deteriorated by residual oxygen. A storable package is provided.

Patent documents are as follows.
Japanese Patent Laid-Open No. 11-12115 Japanese Unexamined Patent Publication No. 7-187255

However, it is impossible to completely block the mixing of oxygen at the time of filling and the ingress of oxygen over time. For example, in an oxygen barrier layer such as an aluminum foil, pinholes are generated and oxygen enters when a package is manufactured, filled and packaged, and transported. Oxygen also enters from the heat seal portion of the package. Moreover, industrially, a gas replacement packaging method for removing all oxygen in the head space of the package has not been developed, and there is no apparatus for completely removing dissolved oxygen.

  In addition, oxygen scavengers cannot be used because the components are eluted in the liquid. Also, if there is a sachet in the liquid food, it cannot be used because there is a possibility of accidental ingestion.

Therefore, as a means for removing oxygen that enters or remains inside the package, iron is mixed in a part of the laminate resin layer forming the package, and the package absorbs and removes oxygen in the package. Has been proposed. (Patent Document 2)
However, simply adding an oxygen absorbent such as iron to a part of the resin layer forming the package cannot efficiently remove the dissolved oxygen in the liquid contents, causing the product to be denatured.

  Moreover, when iron is oxidized, it changes into iron oxide. For this reason, the compounded resin layer may crack due to volume expansion, and rust may ooze out or the contents may leak out. In addition, the eluted iron ions may be combined with food ingredients to produce a nasty taste.

  SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and the invention according to claim 1 provides a packaging body with a packaging mounting member exposed both inside and outside the packaging body such as a plug, spout and dispenser. A packaging mounting member capable of removing contents by mounting, wherein all or at least a part of the plug, spout and dispenser is made of a resin composition containing an oxygen absorbent. This relates to an oxygen-absorbing packaging mounting member.

  The invention according to claim 2 relates to an oxygen-absorbing package mounting member according to claim 1, wherein the oxygen absorbent is an inorganic compound in which oxygen defects are formed by performing a reduction treatment. is there.

  The invention according to claim 3 is the oxygen absorption according to claim 1 or 2, wherein the inorganic compound content in the compounded resin of the inorganic compound in which oxygen defects are formed is 0.5 wt% to 50 wt% The present invention relates to a sex packaging mounting member.

  The invention according to claim 4 is characterized in that the inorganic compound in which oxygen defects are formed is titanium dioxide, zinc oxide, cerium oxide, or iron oxide. The present invention relates to a mounting member.

  The invention according to claim 5 is the oxygen absorption according to any one of claims 1 to 4, characterized in that the inorganic compound in which oxygen defects are formed is titanium dioxide having oxygen defects and is a crystal form of anatase. The present invention relates to a sex packaging mounting member.

  According to a sixth aspect of the present invention, when the oxygen-absorbing package mounting member according to any one of the first to fifth aspects is mounted on a package, at least a portion of the package mounting member contained within the package is oxygen. Oxygen absorption characterized by comprising a resin composition blended with an absorbent, and a part capable of preventing oxygen permeation from the outside being applied to the part where the packaging mounting member is exposed to the outside of the package The present invention relates to a sex packaging mounting member.

  A seventh aspect of the present invention relates to a package comprising the oxygen-absorbing package mounting member according to any one of the first to sixth aspects.

The invention according to claim 8 relates to the package according to claim 7, characterized in that a resin composition layer containing an oxygen absorbent is provided inside the oxygen barrier layer forming the package.

  In the invention of claim 9, the oxygen barrier layer is an aluminum layer, an alumina vapor deposition layer, an inorganic compound vapor deposition layer, a polyvinyl acetate, or a part or complete saponified product of an ethylene-vinyl acetate copolymer, polyester, polyamide, polyvinylidene chloride. It is formed from resin excellent in oxygen barrier properties, such as polyacrylonitrile, The packaging body of Claim 7 or Claim 8 characterized by the above-mentioned.

  According to the first and second aspects of the present invention, the oxygen-absorbing packaging mounting member directly contacts the liquid contents, so that dissolved oxygen in the product can be efficiently removed. In addition, unlike the reduced iron, the inorganic compound in which oxygen defects are formed according to the present invention is not accompanied by a large change in crystal structure before and after oxygen absorption, so that the compounded resin layer cracks due to volume expansion, contents leak, There is no occurrence of such as.

  According to the invention of claim 3, it is possible to maintain the physical properties as a packaging mounting member and obtain an oxygen-absorbing packaging mounting member.

  According to the invention of claim 6, by preventing permeation of oxygen, oxygen inside the package can always be maintained at a low concentration, and quality assurance of products over a long period can be made possible.

  According to the inventions of claims 7 to 9, it becomes possible to obtain a package equipped with an oxygen-absorbing package-mounting member, and further, deterioration of the contents due to oxygen by blocking the entry of oxygen from the outside. Can be prevented.

  The inorganic compound that forms the above-described oxygen defect according to the present invention is obtained by heating a normal inorganic compound in an oxygen-free atmosphere or irradiating ultraviolet rays, and the production method is not particularly limited.

  The shape is not particularly limited, and may be granular, spherical, plate-like, columnar, cylindrical, powdery, granular, etc., but has a large surface area and a granular or powdery form having a high oxygen absorption rate. Are more preferred.

  The size of the inorganic compound that forms oxygen defects used in the present invention is not particularly limited, but is preferably about 10 to 10 μm in consideration of dispersibility in the compounded resin and the like.

  The content of the inorganic compound that forms oxygen defects used in the present invention is preferably 0.5% by weight to 50% by weight. If it is less than this, sufficient oxygen absorption ability cannot be obtained, and if it is more than this, the compounded resin layer becomes brittle, and the strength as a packaging member may not be maintained.

  The proportion of oxygen defects in the inorganic compound that forms oxygen defects used in the present invention is preferably that from which 0.01% to 25% of oxygen is released. If the ratio of oxygen defects is lower than this, it becomes 1 ml or less per 1 mol of the inorganic compound and sufficient oxygen absorption capacity cannot be obtained, and if it is larger than this, a phenomenon that the oxygen absorption capacity decreases is not preferable.

In particular, the titanium dioxide having oxygen defects used in the present invention may be crystalline or amorphous such as rutile or brookite, but more preferably anatase type from the viewpoint of oxygen absorption rate.

  As the method for forming the oxygen-absorbing packaging mounting member according to the present invention, various molding methods such as a direct blow molding method, an injection molding method, a multicolor injection molding method, a co-injection molding method, and an insert molding method are used. Things are possible. Of the molded packaging mounting member, a portion made of a resin composition containing an oxygen absorbent directly contacts the liquid contents, so that dissolved oxygen in the product can be efficiently absorbed.

  As a resin material used for obtaining a packaging mounting member containing the above-mentioned oxygen absorbent, polyolefin such as low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, or polyester, polyamide, polyvinyl chloride, etc. Is preferred.

  In consideration of development on the package, it is preferable to remove as much oxygen as possible from the outside. Therefore, it is better to provide a barrier layer having low oxygen permeability as the packaging member. In particular, the portion exposed to the outside of the package (see FIGS. 5, 6, 7, and 8) is covered with a barrier film having low oxygen permeability, or is coated with alumina, an inorganic compound, or organosilane by a CVD deposition method. By doing so, regardless of the shape of the oxygen-absorbing packaging mounting member, it is possible to block the entry of oxygen from the outside and to keep the oxygen inside the packaging body always at a low concentration.

  As an oxygen barrier layer for forming a package, in addition to an aluminum layer, an alumina vapor deposition layer by PVD vapor deposition, an inorganic compound vapor deposition layer, a CVD vapor deposition layer using organosilane such as hexamethylenedisiloxane as a raw material, or an oxygen permeation layer For example, polyvinyl acetate or ethylene-vinyl acetate copolymer part or completely saponified product, polyester, polyamide, polyvinylidene chloride, polyacrylonitrile, etc., are not limited to these examples. Absent.

  Since the packaging member according to the present invention has a normal configuration except that an inorganic compound-containing resin layer that forms oxygen defects is provided, it can be manufactured with existing equipment.

  Further, the packaging mounting member according to the present invention is economical because it can be molded by existing equipment.

  The following examples illustrate the invention.

  Using an injection molding machine, an oxygen-absorbing spout of this example shown in FIG. 2 was obtained. In this spout, the resin composition (2) containing the oxygen absorbent is in direct contact with the liquid contents. An oxygen barrier property was imparted to the portion (1) exposed to the outside of the package made of high-density polyethylene by a CVD vapor deposition method. In a spout composed of about 10 g of high density polyethylene (2) containing 25 wt% of an oxygen absorber, the oxygen absorber used was a particle size of 200 nm from which 10% of oxygen in anatase-type titanium dioxide that forms oxygen defects was released. I used something.

Using an injection molding machine, the oxygen-absorbing spout of this example shown in FIG. 3 was obtained. In this spout, the resin composition (3) containing the oxygen absorbent does not directly contact the liquid contents. An oxygen barrier property was imparted to the portion (1) exposed to the outside of the package made of high-density polyethylene by a CVD vapor deposition method. In a spout composed of about 10 g of high density polyethylene (3) blended with 25 wt% of an oxygen absorbent, the oxygen absorbent used was a particle size of 200 nm from which 10% of oxygen of anatase-type titanium dioxide forming oxygen defects was released. I used something.

  From the outer layer, the body film is “polyethylene (15 μm) (6) / printing / alumina-deposited polyester film (15 μm) (7) / 25 wt% oxygen absorbent blended polyethylene (30 μm) (8) / polyethylene (15 μm) (9) In the configuration, a pouch with a spout of Example 1 in the packaging mounting member was obtained, and a spout with a spout of 200 × 100 mm was obtained by bonding the spout of Example 1 to the shoulder of the pouch by heat fusion (FIG. 5). FIG. 6). As the oxygen absorber used for the trunk film, an oxygen absorber having a particle diameter of 200 nm from which 10% of oxygen of anatase-type titanium dioxide forming oxygen defects was released was used.

  From the outer layer, the body film is “polyethylene (15 μm) (6) / printing / alumina-deposited polyester film (15 μm) (7) / 25 wt% oxygen absorbent blended polyethylene (30 μm) (8) / polyethylene (15 μm) (9) In the configuration, a pouch with a spout of Example 2 in which the packaging mounting member was a pouch with a spout of Example 2 was obtained by bonding the spout of Example 2 to the shoulder of the pouch by heat fusion. As the oxygen absorber used for the trunk film, an oxygen absorber having a particle diameter of 200 nm from which 10% of oxygen of anatase-type titanium dioxide forming oxygen defects was released was used.

<Comparative example 1> The spout which has the oxygen absorptivity of this comparative example was obtained using the injection molding machine. An oxygen barrier property was imparted to the portion exposed to the outside of the package made of high-density polyethylene by a CVD method. In a spout composed of about 10 g of high-density polyethylene containing 10 wt% of an oxygen absorbent, the oxygen absorbent used was reagent grade reduced iron and 1 wt% of sodium chloride was added as a reaction accelerator.

<Comparative example 2> The spout which has the oxygen absorptivity of this comparative example was obtained using the injection molding machine. The part exposed to the outside of the package made of high-density polyethylene was not subjected to a treatment for blocking the entry of oxygen. In a spout made of about 10 g of high-density polyethylene containing 25 wt% oxygen absorber, the oxygen absorber used is one with a particle size of 200 nm from which 10% oxygen of anatase-type titanium dioxide that forms oxygen defects is released. did.

Comparative Example 3 A spout of this comparative example was obtained using an injection molding machine. An oxygen barrier property was imparted to the portion exposed to the outside of the package made of high-density polyethylene by a CVD method. In a spout consisting of about 10 g of high density polyethylene, no oxygen absorber was blended.

<Comparative Example 4> The body film is formed of “polyethylene (15 μm) / printing / alumina-deposited polyester film (15 μm) / 10 wt% oxygen absorbent-containing polyethylene (30 μm) / polyethylene (15 μm)” from the outer layer for packaging mounting. In the pouch with a spout of Comparative Example 1, a spout with a spout of 200 × 100 mm in which the spout of Comparative Example 1 was bonded to the shoulder of the pouch by thermal fusion was obtained. The oxygen absorber used for the trunk film was reagent grade reduced iron, and 1 wt% sodium chloride was added as a reaction accelerator.

<Comparative Example 5> The body film is formed of “polyethylene (15 μm) / printing / alumina-deposited polyester film (15 μm) / 25 wt% oxygen absorbent-containing polyethylene (30 μm) / polyethylene (15 μm)” from the outer layer, for package mounting. In the pouch with a spout of Comparative Example 2, a 200 × 100 mm pouch with a spout was obtained, in which the spout of Comparative Example 2 was bonded to the shoulder of the pouch by thermal fusion. As the oxygen absorber used for the trunk film, an oxygen absorber having a particle diameter of 200 nm from which 10% of oxygen of anatase-type titanium dioxide forming oxygen defects was released was used.

<Comparative example 6> Body film is "polyethylene (15 µm) / printing / alumina-deposited polyester film (15 µm) / 25 wt% oxygen absorbent-containing polyethylene (30 µm) / polyethylene (15 µm)" from the outer layer for packaging mounting In the pouch with a spout of Comparative Example 3, the spout with a spout of Comparative Example 3 was bonded to the shoulder of the pouch by thermal fusion to obtain a 200 × 100 mm pouch with a spout. As the oxygen absorber used for the trunk film, an oxygen absorber having a particle diameter of 200 nm from which 10% of oxygen of anatase-type titanium dioxide forming oxygen defects was released was used.

<Comparative example 7> In the pouch with the spout of the comparative example 3, the trunk | drum film is a structure of "polyethylene (15 micrometer) / printing / alumina vapor deposition polyester film (15 micrometer) / polyethylene (45 micrometer)" from an outer layer, A 200 × 100 mm pouch with a spout obtained by bonding the spout of Comparative Example 3 to the shoulder portion of the pouch by heat-sealing was obtained.

  <Test 1> The spouts of Examples 1 and 2 and Comparative Examples 1 to 3 obtained using an injection molding machine were put in an aluminum pouch filled with water (100 ml) and sealed. The head space capacity of the obtained pouch was about 10 ml. The dissolved oxygen concentration of the filled water was 8.0 ppm. This was stored at 25 ° C. for 2 weeks, and the oxygen concentration in the head space was measured using an oxygen concentration meter, and the dissolved oxygen concentration of water was measured using a dissolved oxygen meter. The results are shown in Table 1.

  <Test 2> The obtained pouch (FIGS. 5 and 6) was filled with water (200 ml) from the drinking mouth and then sealed to obtain a filled product. The head space capacity was about 10 ml. The dissolved oxygen concentration of the filled water was 8.0 ppm. This was stored at 25 ° C. for 2 weeks, and the oxygen concentration in the head space was measured using an oxygen concentration meter, and the dissolved oxygen concentration of water was measured using a dissolved oxygen meter. The results are shown in FIGS.

  <Test 3> The obtained pouch was similarly filled with a beverage and sealed. The head space capacity was about 10 ml. As the beverage, orange juice was used, which was sterilized at 98 ° C. for 30 seconds using a plate-type sterilizer in an aseptic environment. This was stored in a 34 ° C. environment for 3 months, and the oxygen concentration, dissolved oxygen concentration, and amount of reduced ascorbic acid in the headspace were measured. The indophenol method was used to measure the amount of reduced ascorbic acid. Moreover, it evaluated by the sensuality. The state of the packaging material was also observed.

  According to the result of Test 1, the packaging mounting member made of the resin composition containing titanium dioxide that forms oxygen defects according to the present invention absorbs oxygen in the same manner as the conventional iron-based oxygen absorbent, and further dissolves. It was shown that oxygen is also absorbed efficiently.

According to the result of Test 2, the packaging mounting member made of a resin composition containing titanium dioxide that forms oxygen defects is combined with the body film including the barrier layer to efficiently remove oxygen and dissolved oxygen in the headspace. To be confirmed. However, when the treatment for imparting oxygen barrier properties to the portion exposed to the outside of the package is not performed, both the head space oxygen and the dissolved oxygen are once reduced, but thereafter there is a tendency that the oxygen concentration gradually increases.

  According to the result of Test 3, a package equipped with a packaging mounting member made of a resin composition containing titanium dioxide that forms oxygen defects according to the present invention has a pinhole caused by “rust” found in iron-based oxygen absorbers. There was no occurrence, and it was shown that the contents were excellent in storage stability. In addition, it was considered that the oxygen concentration in the head space and the decrease in dissolved oxygen in Comparative Examples 6 and 7 were reduced because the oxygen mixed during filling was used for the oxidation of the content components.

  In the present invention, only spout was used, but by changing the resin and molding method used, it was developed into an oxygen-absorbing dispenser shown in FIG. 4 and a plastic bottle container (see FIGS. 7 and 8) equipped with the dispenser. Is possible as well.

  The present invention relates to a packaging mounting member that is exposed both inside and outside of a packaging body such as a plug, spout and dispenser, comprising a resin composition containing an oxygen absorbent and a thermoplastic resin, and the packaging thereof. It is used as a technique related to a package with a mounting member.

It is a conceptual perspective view which shows an example in case the mounting member for packaging of this invention is a spout. It is a partial conceptual sectional view showing an example of the spout of FIG. It is a partial conceptual sectional view showing an example of the spout of FIG. 1 different from FIG. It is a conceptual perspective view which shows an example in case the mounting member for packaging of this invention is a dispenser. It is a front conceptual sectional view of the package which shows the state where the spout of Drawing 1 was equipped. It is a partial expanded sectional view of the package of FIG. It is a front conceptual sectional drawing of the package which shows the state with which the dispenser of FIG. 4 was mounted | worn. It is a partial expanded sectional view of the package of FIG. It is a graph which shows the result of having measured the oxygen concentration in a head space using the oxygen concentration meter. It is a graph which shows the result of having measured the dissolved oxygen concentration of water using the dissolved oxygen meter.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Polyethylene container 2 ... Extraction port 3 ... Opening part 4 ... Polypropylene cap 5 ... Thin film 6 ... Seal part 7 ... Boat shape 8 ... Cylindrical part 9 ... Boat shape top surface

Claims (9)

  In the packaging mounting member capable of taking out the contents by mounting on the packaging body, all or at least a part of the packaging mounting member is made of a resin composition containing an oxygen absorbent. An oxygen-absorbing packaging mounting member.   The oxygen-absorbing packaging mounting member according to claim 1, wherein the oxygen absorbent is an inorganic compound in which oxygen defects are formed by performing a reduction treatment.   The oxygen-absorbing packaging and mounting member according to claim 1 or 2, wherein an inorganic compound content in the compounded resin of the inorganic compound in which oxygen defects are formed is 0.5 wt% to 50 wt%.   The oxygen-absorbing packaging mounting member according to any one of claims 1 to 3, wherein the inorganic compound in which oxygen defects are formed is titanium dioxide, zinc oxide, cerium oxide, or iron oxide.   5. The oxygen-absorbing packaging mounting member according to claim 1, wherein the inorganic compound having an oxygen defect is titanium dioxide having an oxygen defect and is anatase crystal.   A resin composition in which an oxygen absorbent is blended in at least a portion of the packaging mounting member when the oxygen-absorbing packaging mounting member according to any one of claims 1 to 5 is mounted on the packaging body. An oxygen-absorbing package mounting member, characterized in that a portion of the package mounting member exposed to the outside of the package is subjected to a treatment capable of preventing oxygen permeation from the outside.   A package comprising the oxygen-absorbing packaging mounting member according to any one of claims 1 to 6.   8. The package according to claim 7, wherein a resin composition layer containing an oxygen absorbent is provided on the inner side of the oxygen barrier layer of the laminate forming the package.   Oxygen barrier layer is an aluminum layer, alumina vapor deposition layer, inorganic compound vapor deposition layer, or oxygen barrier such as polyvinyl acetate or partially or completely saponified ethylene-vinyl acetate copolymer, polyester, polyamide, polyvinylidene chloride, polyacrylonitrile, etc. The package according to claim 7 or 8, wherein the package is formed from a resin having excellent properties.

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