JP2019095223A - Oxygen absorption capacity measuring device, method for measuring oxygen absorption capacity, and method for manufacturing articles - Google Patents

Abstract

To provide an oxygen absorption capacity measuring device for accurately measuring the oxygen absorption capacity of an article, a method for measuring an oxygen absorption capacity using the device, and a method for manufacturing an article.SOLUTION: An oxygen absorption capacity measuring device 10 includes: a constant temperature and humidity container 4; a pressure resistance container 3; and an oxygen concentration meter 2, the pressure resistance container 3 being located in the constant temperature and humidity container 4 and having a space for containing an article 1 as a target of measurement of the oxygen absorption capacity, and the oxygen concentration meter 2 being arranged to be capable of measuring the concentration of the oxygen in the space.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an oxygen absorbing capacity measuring device, a method of measuring oxygen absorbing capacity, and a method of manufacturing an article.

The quality of food and medicines is degraded by oxidation. For this reason, a film having an ability to absorb oxygen is used as a packaging material for food and medicine. Bags, containers and the like made of this film are used as packaging for food and medicine.
When selecting a film to be used for such packaging, a means capable of accurately measuring the oxygen absorption capacity of the film is required.

In Patent Document 1, a film is sandwiched between the first apparatus main body and the second apparatus main body, oxygen gas is supplied to the gas flow chamber of the first apparatus main body, nitrogen is supplied to the gas flow chamber of the second apparatus main body, We have proposed an oxygen permeability measuring device that measures the concentration of oxygen flowing into the gas flow chamber of the device body.
Patent Document 2 proposes an oxygen permeability measuring device having a chemiluminescent substance that is oxidized by oxygen to cause chemiluminescence and a photon detection unit that detects photons emitted from the chemiluminescent substance.

Unexamined-Japanese-Patent No. 2005-233943 JP, 2011-214840, A

However, in the device of Patent Document 1, it can not be clearly distinguished whether it has oxygen barrier property or oxygen absorbing ability.
Further, in the device of Patent Document 2, since photons can not be detected unless the film has light transparency, it can not be used for a film containing aluminum foil or the like.
The present invention has been made in view of the above circumstances, and an oxygen absorbing capacity measuring apparatus capable of accurately measuring the oxygen absorbing capacity of an article, a method of measuring an oxygen absorbing capacity using the same, and a method of manufacturing the article To aim.

As a result of intensive studies, the present inventors have found that the following apparatus can solve the above-mentioned problems.
That is, the present invention has the following aspects.
[1] constant temperature and humidity container,
Pressure-resistant container,
And an oximeter,
The pressure container is located in the constant temperature and humidity container;
The pressure container has a space for housing an article whose oxygen absorption capacity is to be measured,
The oxygen absorbing capacity measuring device, wherein the oximeter is arranged to measure oxygen concentration in the space.
[2] An article for measuring the oxygen absorption capacity is disposed in the pressure container of the oxygen absorption capacity measurement device according to [1],
Measuring the oxygen concentration of the space with the oximeter, and calculating the amount of oxygen absorbed by the article from the oxygen concentration.
[3] The method for producing an article according to [2], wherein the volume of the article is 0.5 to 50% by volume with respect to the volume of the pressure container.
[4] The method for producing an article according to [2] or [3], wherein the article is aged at a temperature of 20 to 60 ° C. and a humidity of 40 to 90% RH for 15 to 60 minutes.
[5] The method for producing an article according to any one of [2] to [4], wherein the article contains an oxygen absorbent.
[6] The method for producing an article according to any one of [2] to [5], wherein the article is a laminated film.
[7] A method of manufacturing an article, comprising measuring the oxygen absorption capacity of the article by the method of measuring oxygen absorption capacity according to any one of [2] to [6].

  According to the present invention, it is possible to provide an oxygen absorbing capacity measuring device capable of accurately measuring the oxygen absorbing capacity of an article, a method of measuring an oxygen absorbing capacity using the same, and a method of manufacturing an article.

It is a perspective view showing an example of the oxygen absorption capacity measuring device of the present invention.

«Oxygen absorption capacity measuring device»
The oxygen absorption capacity measuring device of the present invention has a constant temperature and humidity chamber, a pressure container, and an oximeter.
The oxygen absorption capacity measuring device 10 of FIG. 1 has a constant temperature and humidity container 4, a pressure container 3 and an oximeter 2. The pressure resistant container 3 is located in the constant temperature and humidity container 4. The pressure-resistant container 3 has a space for containing the article 1 whose oxygen absorption capacity is to be measured. The oximeter 2 is accommodated in the pressure container 3 in order to measure the oxygen concentration in the space.

The constant temperature and humidity container 4 preferably has temperature control means for controlling the temperature and humidity control means for controlling the humidity.
The pressure-resistant container 3 may be airtight as well as having pressure resistance, and examples thereof include a desiccator and the like.
The position of the oximeter 2 is not limited as long as the oxygen concentration in the pressure container can be measured. For example, the sensor portion for detecting the oxygen concentration may be located in the pressure container 3, and the oximeter main body may be located in the pressure container 3, or may be located outside the pressure container 3 Good. As the oxygen concentration meter 2, a zirconia type, a magnetic type or the like may be used. Moreover, it is preferable that the oximeter 2 has a data logging function which measures oxygen concentration and stores data, when fixed time progress passes.

The volume of the constant temperature and humidity container 4 is not limited as long as the pressure container 3 can be stored, but 2,000 to 800,000 cm ³ is preferable, and 5,000 to 500,000 cm ³ is more preferable.
The volume of the pressure container 3 is not limited as long as it can store an article and an oximeter, but in consideration of storage in a constant temperature and humidity chamber, 1,500 to 20,000 cm ³ is preferable, and 3,000 to 10,000 cm ^3. Is more preferred.
3: 1-30: 1 are preferable and, as for the volume ratio represented by the volume of the constant temperature / humidity container / the volume of a pressure container, 5: 1-20: 1 are more preferable. When the volume ratio is in the above range, the temperature and humidity can be easily adjusted, and the oxygen absorption capacity of the article can be measured more accurately.

«Measurement method of oxygen absorption capacity»
The method of measuring the oxygen absorption capacity of the present invention is a method of measuring the oxygen absorption capacity of an article using the oxygen absorption capacity measuring device of the present invention.
The method of measuring the oxygen absorption capacity of the present invention comprises the steps of arranging an article for measuring the oxygen absorption capacity in the pressure container of the oxygen absorption capacity measuring apparatus of the present invention, measuring the oxygen concentration in the space in the pressure container And calculating the amount of oxygen absorbed by the article from the oxygen concentration.

In the step of arranging the article for measuring the oxygen absorption capacity in the pressure resistant container of the oxygen absorption capacity measuring device of the present invention, the article is preferably arranged such that the entire surface is in contact with the gas in the pressure resistant container. By arranging in this manner, the oxygen absorption capacity of the article can be measured more accurately.
The volume of the article is preferably 0.5 to 50% by volume, more preferably 1 to 30% by volume, with respect to the volume of the pressure resistant container. If the volume of the article is in the above range, the oxygen absorption capacity of the article can be measured more accurately.

  In the step of measuring the oxygen concentration in the space in the pressure container with an oximeter, the oximeter may be set to measure the oxygen concentration at regular intervals. Thereby, the oxygen absorption capacity of the article can be continuously observed in time series.

In the step of calculating the amount of oxygen absorbed by the article from the oxygen concentration, the amount of oxygen absorbed by the article is calculated from the following equation (1) based on the oxygen concentration measured by the oximeter and the volume of the pressure container.
Amount of oxygen absorbed by the article (cm ³ ) = reduced oxygen concentration (vol%) × volume of pressure resistant container (cm ³ ) (1)

The method of measuring the oxygen absorption capacity of the present invention may include the step of adjusting the temperature and humidity in the constant temperature and humidity chamber. 20-80 degreeC is preferable and, as for the temperature in a constant temperature and humidity container, 40-60 degreeC is more preferable. The humidity in the constant temperature and humidity container is preferably 25 to 90% RH, and more preferably 50 to 75% RH.
Moreover, the measuring method of the oxygen absorption capacity of this invention may include the process of filling the space in a pressure-resistant container with oxygen gas.
10 to 100 volume% is preferable with respect to the volume of a pressure-resistant container, and, as for the ratio of the oxygen gas in a pressure-resistant container, 15 to 50 volume% is more preferable. By setting the oxygen gas concentration within the above numerical range, it is possible to more accurately measure the oxygen absorbing ability even for an article having high oxygen absorbing ability.
It is preferable to set measurement time to 1 to 45 days, and it is more preferable to set to 1 to 15 days. By setting the measurement time within the above range, the maximum amount of oxygen absorption of the article can be calculated.

Preferably the article comprises an oxygen absorber. The oxygen absorbing ability can be exhibited by containing the oxygen absorbent.
A well-known material can be used as an oxygen absorbent. Examples of the oxygen absorber include transition metal salts and compounds having a carbon-carbon double bond. The transition metal salt also has a function as an oxygen absorption catalyst.
Examples of the transition metal salt include iron salts, nickel salts, copper salts, manganese salts, cobalt salts, rhodium salts, titanium salts, chromium salts, vanadium salts and ruthenium salts. Among these, iron salts, nickel salts, copper salts, manganese salts and cobalt salts are preferable, manganese salts and cobalt salts are more preferable, and cobalt salts are more preferable.
As the anion constituting the transition metal salt, an organic acid is preferable. For example, acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, tall acid, oleic acid, resin acid , Capric acid and naphthenic acid.
As the transition metal salt, cobalt neodecanoate and cobalt oleate are preferable.

As a conjugated diene polymer, the homopolymer or copolymer of a conjugated diene monomer, or the copolymer of a conjugated diene monomer and another monomer is mentioned. As said other monomer, the monomer copolymerizable with the said conjugated diene monomer is mentioned.
As a conjugated diene monomer, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like. One of these monomers may be used alone, or two or more thereof may be used in combination. Among these, 1,3-butadiene and isoprene are preferable, and isoprene is more preferable.
The monomer copolymerizable with the conjugated diene monomer is not particularly limited. Examples thereof include aromatic vinyl monomers such as styrene, methylstyrene, dimethylstyrene, ethylstyrene, butylstyrene, chlorostyrene and bromostyrene. Linear olefin monomers such as ethylene, propylene and 1-butene; cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclo Nonconjugated diene monomers such as pentadiene and 5-ethylidene-2-norbornene; (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; (meth) acrylonitrile, (meth) acrylamide and the like Can be mentioned. One of these monomers may be used alone, or two or more thereof may be used in combination.
As a conjugated diene polymer, natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR), ethylene-propylene-diene type Copolymer rubber, butadiene-isoprene copolymer rubber (BIR) and the like can be mentioned. Among them, polyisoprene rubber and polybutadiene rubber are preferable, and polyisoprene rubber is more preferable.

The conjugated diene polymer cyclized product is obtained by subjecting a conjugated diene polymer to a cyclization reaction in the presence of an acid catalyst.
As an acid catalyst used for the cyclization reaction, for example, sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, alkylbenzenesulfonic acid having an alkyl group having 2 to 18 carbon atoms, or the like Organic sulfonic acid compounds such as anhydrides or alkyl esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, ethyl ammonium dichloride, aluminum bromide, antimony pentachloride, six And metal halides such as tungsten chloride and iron chloride; One of these acid catalysts may be used alone, or two or more thereof may be used in combination.
The glass transition temperature (Tg) of the conjugated diene polymer cyclized product is not particularly limited, but is preferably in the range of 0 to 100 ° C, more preferably 30 to 70 ° C.

  The content of the oxygen absorber is preferably 1 to 100% by mass, and more preferably 5 to 50% by mass, with respect to the total mass of the article. When the content of the oxygen absorbent is equal to or more than the above lower limit value, it becomes easier to improve the oxygen absorbing ability of the article. When the content of the oxygen absorbent is less than or equal to the above upper limit value, the handleability of the article can be more easily improved.

The article is preferably a laminated film. The laminate film preferably has a sealant material comprising a laminate layer, a seal layer, and an intermediate layer.
The intermediate layer is disposed between the laminate layer and the seal layer.

<Laminated layer>
The resin constituting the laminate layer is not particularly limited. For example, polyethylene (PE) such as low density polyethylene (LDPE), linear LDPE (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), etc. Examples thereof include polypropylene (PP) such as axially-oriented polypropylene (OPP) and non-oriented polypropylene (CPP), copolymers of ethylene and propylene, and ethylene-butene-1 copolymers.
Among these, any one may be used alone, or two or more may be used in combination.

<Sealing layer>
As a resin which comprises a sealing layer, the thing similar to what was described by the said <lamination layer> is mentioned.

<Middle class>
The intermediate layer 26 is preferably a layer containing at least one selected from ethylene-vinyl alcohol polymer (EVOH), polyvinyl alcohol (PVOH), and xylylene diamine-based polyamide resin.
When the laminated film contains an oxygen absorbent, the intermediate layer preferably contains an oxygen absorbent.

An adhesive layer may be provided between the intermediate layer and the laminate layer. By providing the adhesive layer, the integrity of the intermediate layer and the laminate layer is further enhanced, and the impact resistance is easily enhanced.
An adhesive layer may be provided between the intermediate layer and the seal layer. By providing the adhesive layer, the integrity of the intermediate layer and the seal layer is further enhanced, and the impact resistance is likely to be enhanced.
As materials constituting the adhesive layer, conventionally known materials can be used, and examples thereof include polyurethane-based, polyester-based, epoxy-based, polyvinyl acetate-based, acid-modified polyolefin-based adhesives, titanate-based, polyurethane-based, Examples of the anchor coating agent include polyethylene imine type and polybutadiene type. These materials may be used alone or in combination of two or more.

When the article is a laminated film, it is preferred to include a substrate in addition to the sealant material.
Examples of the substrate include resin films, metal foils, paper, and laminates of these.
Examples of resin films include polyethylene terephthalate (PET) such as biaxially oriented polyethylene terephthalate, biaxially oriented polypropylene (OPP), non-oriented polypropylene (CPP), high density polyethylene (HDPE), and polyolefin such as medium density polyethylene (MDPE) And polyamide (PA) such as biaxially oriented nylon (ONY), and laminates thereof. Among them, PET, OPP and nylon (NY) are preferable.
Moreover, the vapor deposition film in which metal, such as aluminum, or silica was vapor-deposited by the said resin films may be used as a base material. Among them, metal-deposited films in which metal is deposited on PET, OPP, ONY are preferable, and aluminum-deposited films are more preferable.
As metal foil, aluminum foil is preferable.
As a laminated body, the laminated body of the said resin-made films, and the laminated body of the said resin-made films and metal foil are mentioned. These may be laminated with an adhesive.
The substrate may be printed on its surface or between layers.

An adhesive layer may be provided between the substrate and the sealant layer. By providing the adhesive layer, the integrity of the substrate and the sealant layer is further enhanced, and the impact resistance is easily enhanced.
As a material which comprises an adhesive layer, the thing similar to what was mentioned by description of the adhesive layer of the said sealant material can be used.

  The article is preferably aged at a temperature of 20 to 60 ° C. and a humidity of 40 to 90% RH for 15 to 60 minutes. By using such an article, it is possible to suppress the variation in the oxygen absorbing ability and to more accurately measure the oxygen absorbing ability of the article.

«Product manufacturing method»
The method of manufacturing the article of the present invention includes the step of measuring the oxygen absorption capacity of the article by the method of measuring the oxygen absorption capacity of the present invention.

The method for producing an article of the present invention preferably includes the step of curing the article at a temperature of 20 to 60 ° C. and a humidity of 40 to 90% RH for 15 to 60 minutes. By curing, variations in oxygen absorbing ability can be suppressed, and the oxygen absorbing ability of the article can be measured more accurately.
The curing step is preferably performed before the step of measuring the oxygen absorption capacity of the article.

When the article is a laminated film having a sealant material, the method for producing the article of the present invention preferably includes the step of forming the sealant material.
In the case where the article is a sealant material and a laminated film having a substrate, the method for producing an article of the present invention comprises the steps of forming a sealant material, forming a substrate, and laminating the sealant material and the substrate. It is preferable to include.

  EXAMPLES The present invention will be described in more detail using the following examples, but the present invention is not limited to these examples.

As a laminated film for measuring oxygen absorption ability, laminated film A consisting of LDPE (20 μm) / oxygen absorbing material (10 μm) / LDPE (20 μm), PET (12 μm) / adhesive layer (2 μm) / aluminum foil (7 μm) / A laminated film B consisting of an adhesive layer (2 μm) / laminated film A (50 μm) was prepared. The laminated film A and the laminated film B were cut into test pieces so as to have a volume of 500 cm ³ .
Pressure-resistant container containing an oximeter (trade name "OXYMAN Plus" manufactured by Taiyo Engineering Co., Ltd.) in a constant temperature and humidity container (trade name "THE051A" manufactured by Advantec Toyo Kaisha, Ltd., volume: 120,000 cm ³ ) (Trade name “vacuum desiccator VS type”, manufactured by As One Corporation, volume: 7,000 cm ³ ) was disposed to make an oxygen absorption capacity measuring device.
The interior of the constant temperature and humidity chamber was adjusted to 40 ° C. and 75% RH, and the laminated film A was allowed to stand for 30 minutes in the constant temperature and humidity chamber for curing.
The laminated film A was taken out, the oximeter and the laminated film A were placed in a pressure resistant container, and measurement of the oxygen concentration was started. The oximeter was set to measure oxygen concentration every 30 minutes.
Immediately after the measurement was started, the temperature and humidity control container was adjusted to 60 ° C. and 50% RH.
After 8 days from the start of measurement, the oximeter was stopped and measurement of oxygen concentration was finished.
After curing the laminated film B in the same manner, the oxygen absorption capacity was measured. After 15 days from the start of the measurement, the oximeter was stopped and measurement of oxygen concentration was finished.

As a result of oxygen concentration measurement, laminated film A reduced the oxygen concentration in the pressure resistant container to less than 5% on the eighth day of measurement. The oxygen absorption amount of the laminated film A was calculated to be 1,120 cm ³ .
On the other hand, the laminated film B reduced the oxygen concentration in the pressure container to less than 5% on the 15th day of measurement. The oxygen absorption amount of the laminated film B was calculated to be 1,120 cm ³ .
From this, it was found that the oxygen absorption amounts of the laminated film A and the laminated film B including the laminated film A were the same. However, it was found that the laminated film B had a slower oxygen absorption rate.

Reference Signs List 1 article 2 oximeter 3 pressure container 4 constant temperature and humidity container 10 oxygen absorption capacity measuring device

Claims (7)

Constant temperature and humidity container,
Pressure-resistant container,
And an oximeter,
The pressure container is located in the constant temperature and humidity container;
The pressure container has a space for housing an article whose oxygen absorption capacity is to be measured,
The oxygen absorbing capacity measuring device, wherein the oximeter is arranged to measure oxygen concentration in the space. Placing an article for measuring the oxygen absorption capacity in the pressure container of the oxygen absorption capacity measurement apparatus according to claim 1;
Measuring the oxygen concentration of the space with the oximeter, and calculating the amount of oxygen absorbed by the article from the oxygen concentration.   The method for producing an article according to claim 2, wherein the volume of the article is 0.5 to 50% by volume with respect to the volume of the pressure container.   The method for producing an article according to claim 2, wherein the article is aged at a temperature of 20 to 60 ° C. and a humidity of 40 to 90% RH for 15 to 60 minutes.   The method for producing an article according to any one of claims 2 to 4, wherein the article comprises an oxygen absorbent.   The method for producing an article according to any one of claims 2 to 5, wherein the article is a laminated film.   A method of manufacturing an article, comprising measuring the oxygen absorption capacity of the article by the method of measuring oxygen absorption capacity according to any one of claims 2 to 6.

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