JP6202077B2 - Oxygen absorbing materials and packaging materials - Google Patents

Description

  The present invention relates to an oxygen-absorbing material having high transparency and reduced odor generation.

In a package for packaging food or the like, an oxygen-absorbing material that absorbs and removes oxygen inside the package may be used from the viewpoint of maintaining the quality of the content of the food or the like.
As such an oxygen absorbing material, an iron-based oxygen absorbing material containing iron as a main material is known. In general, the iron-based oxygen-absorbing material is enclosed in a sachet and used together with contents such as food in a package.
As an oxygen absorbent, an organic oxygen absorbent using an oxygen-absorbing organic material is known. For example, as described in Patent Document 1, a method of containing an organic oxygen absorbent in any layer of a laminate constituting a package is known.

International Publication No. 2015/146829

However, when the iron-based oxygen-absorbing material is used in the form of a sachet in which the iron-based oxygen-absorbing material is enclosed, there is a possibility that the iron-based oxygen-absorbing material may fall together with the contents when the package is opened. If the contents are food, there is a risk of accidental ingestion with the food.
Further, from the viewpoint of preventing accidental ingestion or the like, it may be added to any layer constituting the package. However, iron-based oxygen-absorbing materials usually have low transparency. For this reason, the package to which the iron-based oxygen absorbing material is added has a problem that the visibility of the contents is lowered.
On the other hand, the organic oxygen-absorbing material has a relatively high transparency. For this reason, the package to which the organic oxygen absorbing material is added has an advantage that the visibility of the contents can be maintained. However, organic oxygen-absorbing materials generate aldehydes and ketones as decomposition products along with the absorption of oxygen, and thus have a problem that a strange odor is generated. In addition, although it is conceivable to separately form a layer for suppressing off-flavors described in Patent Document 1 other than the oxygen absorbing layer, there is a problem that the formation of the package becomes complicated.

  The present invention has been made in view of the above problems, and has as its main object to provide an oxygen-absorbing material that has high transparency and reduced odor generation.

  In order to achieve the above object, the present invention comprises carrier particles and oxygen-absorbing particles supported on the surface of the carrier particles and having a nano-order size, wherein the carrier particles are at least one of metal and silicon. There is provided an oxygen-absorbing material, characterized in that the oxygen-absorbing particles are particles of oxides, nitrides, or oxynitrides of the seed, and the oxygen-absorbing particles are particles of metal or metal oxide having oxygen absorbability.

According to the present invention, the oxygen-absorbing material of the present invention has a configuration in which the oxygen-absorbing particles having a nano-order size are supported on the surface of the carrier particles composed of the above-described highly light-transmitting material. , High transparency.
In addition, since the oxygen-absorbing particles are metal or metal oxide particles having oxygen absorptivity, the oxygen-absorbing material of the present invention has reduced odor generation.
As described above, the oxygen-absorbing material of the present invention has high transparency and reduced odor generation.

  In the present invention, the oxygen-absorbing particles are preferably metal particles having the oxygen-absorbing property. This is because when the constituent material of the oxygen absorbing particles is a metal, the oxygen absorbing particles are excellent in oxygen absorbability.

  In the present invention, the metal having oxygen absorptivity preferably contains at least one of iron, manganese, platinum, aluminum, zinc, tin, magnesium, chromium, silicon, cerium, titanium, and copper. This is because when the constituent material of the oxygen absorbing material is these metals, the oxygen absorbing particles are excellent in oxygen absorbability.

  In the present invention, the average primary particle size of the carrier particles is preferably a nano-order size. This is because when the average primary particle size of the carrier particles is nano-order, the oxygen-absorbing material of the present invention has higher transparency.

  The present invention has a barrier layer and an oxygen absorbing layer disposed on one surface of the barrier layer and containing an oxygen absorbing material, and the oxygen absorbing material is formed on carrier particles and on the surfaces of the carrier particles. And oxygen-absorbing particles having a nano-order size, wherein the carrier particles are particles of at least one oxide, nitride or oxynitride of metal and silicon, and the oxygen-absorbing particles are Provided is a packaging material characterized by being particles of a metal or a metal oxide having oxygen absorbability.

  According to the present invention, since the oxygen absorbing layer contains the above-described oxygen absorbing material, the packaging material of the present invention has high transparency and can reduce odor generation.

  The present invention has an effect of providing an oxygen-absorbing material having high transparency and reduced odor generation.

It is a schematic sectional drawing which shows an example of the packaging material of this invention. It is a schematic sectional drawing which shows the other example of the packaging material of this invention. It is a schematic sectional drawing which shows the other example of the packaging material of this invention.

The present invention relates to an oxygen absorbing material and a packaging material including the same.
Hereinafter, the oxygen absorbing material and the packaging material of the present invention will be described in detail.

A. Oxygen-absorbing material The oxygen-absorbing material of the present invention comprises carrier particles and oxygen-absorbing particles that are supported on the surface of the carrier particles and have a nano-order size, and the carrier particles are at least one of metal and silicon. Oxide, nitride, or oxynitride particles, wherein the oxygen-absorbing particles are oxygen-absorbing metal or metal oxide particles.

According to the present invention, since the oxygen-absorbing particles have a nano-order size, the oxygen-absorbing particles have high transparency even when the oxygen-absorbing particles are composed of a metal having low light transmittance.
Moreover, even if the average primary particle size is nano-order size, the oxygen-absorbing particles are aggregated, and when an oxygen-absorbing particle aggregate having an apparently large particle size is formed, the transparency is lowered.
However, when the oxygen-absorbing particles are supported on the surface of the carrier particles, the oxygen-absorbing particles are held in a state of being dispersed on the surface of the carrier particles, and a decrease in transparency due to aggregation or the like can be suppressed.
Furthermore, since the constituent material of the carrier particles on which the oxygen-absorbing particles are supported is the above-described highly light-transmitting material, for example, even when the particle size of the carrier particles is larger than the particle size of the oxygen-absorbing particles, The carrier particles are highly transparent.
For this reason, a structure in which oxygen absorbing particles having a nano-order size composed of the above-described low light-transmitting material are supported on the surface of carrier particles composed of the above-described highly light-transmitting material. By having the above, the oxygen-absorbing material of the present invention has high transparency.

  In addition, since the oxygen-absorbing particles are oxygen-absorbing metal or metal oxide particles, the oxygen-absorbing material of the present invention has reduced off-flavor generation associated with the formation of aldehydes and ketones, for example. .

  As described above, the oxygen-absorbing material of the present invention has high transparency and reduced odor generation.

The oxygen-absorbing material of the present invention has carrier particles and oxygen-absorbing particles.
Hereafter, each structure of the oxygen absorption material of this invention is demonstrated.

1. Carrier particles The carrier particles in the present invention are particles of at least one oxide, nitride or oxynitride of metal and silicon.
The carrier particles carry oxygen-absorbing particles on the surface.

  Here, “supporting” means that oxygen absorbing particles are attached to the surface of the carrier particles, and usually the carrier particles and oxygen absorbing particles are attached so as to be in direct contact by physical adsorption or the like.

The constituent material of the carrier particles is a metal oxide, nitride or oxynitride, silicon oxide, nitride or oxynitride, or metal and silicon oxide, nitride or oxynitride.
Note that the constituent material is at least one oxide, nitride, or oxynitride of metal and silicon means that at least one oxide, nitride, or oxynitride of metal and silicon (hereinafter, simply referred to as “material”). May be referred to as an oxide or the like) as a main component of the constituent material.
Further, being contained as a main component means that the content of the above-described oxide or the like is higher than 80% by mass of the constituent material.
For example, when the constituent material is an oxide of silicon, the content of silicon oxide can be 80% by mass or more of the constituent material. When the constituent materials are silicon oxide and nitride, the total content of silicon oxide and silicon nitride can be 80% by mass or more.
In the present invention, the content of the above-described oxide or the like is preferably 90% by mass or more of the constituent material, preferably 95% by mass or more, and 100% by mass, that is, the constituent material is the oxidized material. It is preferable that only things are included. This is because the function with the carrier particles can be effectively exhibited.

In the present invention, the constituent material is preferably an oxide, nitride or oxynitride of silicon (Si), or an oxide, nitride or oxynitride of metal and silicon. Si) oxides, nitrides or oxynitrides are preferred, and silicon oxides (silicon oxides) are particularly preferred. This is because the above-described constituent materials, particularly silicon oxide, can form carrier particles having high transparency because of high light transmittance.
In addition, since silicon oxide has a water absorption property, by forming carrier particles using silicon oxide, the carrier particles absorb moisture in the air, etc., so that oxygen absorption ability is expressed with respect to the oxygen absorption particles. Necessary water can be easily supplied. For this reason, the oxygen-absorbing material of the present invention can easily express the oxygen-absorbing ability of the oxygen-absorbing particles.

  The metal used for the metal oxide or the like of the carrier particles may be any metal that can form oxides, nitrides, oxynitrides, and can form carrier particles having a desired light transmittance. Aluminum, zinc, cerium, titanium, indium, calcium, chromium, tin, zirconium, copper, niobium, antimony, etc. are preferable, and aluminum, zirconium, copper are particularly preferable, and aluminum, zirconium are particularly preferable. It is preferable that This is because oxides and the like using the above metals can form carrier particles with high transparency because of high light transmittance. Moreover, the said metal is preferable also from the point of workability, durability, and cost.

  Metal and silicon oxides, nitrides or oxynitrides include oxides, nitrides or oxynitrides containing both metal and silicon elements, specifically silicon aluminum oxynitride (SiAlON), Examples thereof include silicon aluminum oxide (SiAlO).

The types of the constituent materials are not limited to those using only one type, and two or more types may be used. When the number of constituent materials is two or more, for example, carrier particles made of an oxide of silicon as a constituent material and carrier particles made of an oxynitride of a constituent material can be mixed and used.
In the case of two or more types, carrier particles formed from a mixture of both silicon oxide and oxynitride may be used as the carrier particles.

The number of bonds of oxygen and nitrogen constituting the oxide, nitride or oxynitride used for the constituent material to the metal and silicon may be any as long as it can constitute carrier particles having desired light transmittance. For example, for silicon oxide (SiOx), x is greater than 0 and less than or equal to 2.0, for silicon nitride (SiNx), x is greater than 0 and less than or equal to 1.33, and for silicon oxynitride (SiOxNy), x and y can be in the range of more than 0 and 2.0 or less.
In the present invention, the number of bonds of oxygen and nitrogen constituting the oxide, nitride and oxynitride to the metal and silicon is preferably close to the stoichiometric number, and the stoichiometric number is satisfied. It is preferable. The carrier particles have low light absorption in the particle structure, and the refractive index thereof is close to that of the binder resin used for dispersion of the oxygen absorbing material in the oxygen absorbing layer. Because it becomes.
Here, as a thing close | similar to what satisfy | fills a stoichiometric number, it can be set as 90% or more of a stoichiometric number, for example.
For example, when the constituent material is silicon oxide (SiOx), x is preferably 1.8 or more, more preferably 1.9 or more, in particular 2.0. It is preferable that the stoichiometric number is satisfied.

The average primary particle size of the carrier particles may be any as long as it can support oxygen-absorbing particles, and is usually larger than the average primary particle size of oxygen-absorbing particles.
As the average primary particle size of such carrier particles, for example, when used for a packaging material, it may be any material that can be well dispersed in a binder resin, and can be 100 μm or less, and has a nano-order size. It is preferable that This is because when the carrier particles are nano-order size, the oxygen-absorbing material of the present invention has a smaller particle size and higher transparency.
Here, as the nano-order size, for example, the average primary particle size can be 1000 nm or less, preferably 500 nm or less, and in particular within the range of 0.1 nm to 500 nm. It is preferable that it is in the range of 10 nm-300 nm especially. This is because when the average primary particle size is within the above range, the oxygen-absorbing material of the present invention has higher transparency.
In addition, the said average primary particle diameter can be calculated | required by the method of measuring the magnitude | size of a primary particle directly from an electron micrograph. Specifically, a particle image was measured with a transmission electron micrograph (TEM) (for example, H-7650 manufactured by Hitachi High-Tech), and the average length of the longest part of 100 or more randomly selected primary particles. Can be the average primary particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

  The ratio of the average primary particle size of the carrier particles to the average primary particle size of the oxygen-absorbing particles (average primary particle size of the carrier particles / average primary particle size of the oxygen-absorbing particles) may be larger than 1. 10 to 1000, preferably in the range of 20 to 100. This is because the carrier particles can stably support oxygen-absorbing particles when the ratio is within the above-described range.

  The shape of the carrier particles may be any shape that can carry oxygen-absorbing particles, and may be, for example, a spherical shape, an elliptical shape, a cubic shape, or a fiber shape.

  The structure of the carrier particles may be a solid structure having no pores, but is preferably a porous structure having pores. Since the carrier particles have a porous structure, the carrier particles have a larger surface area than that of a solid structure. For this reason, the carrier particles can carry more oxygen-absorbing particles.

  The carrier particles may be subjected to any surface treatment such as a hydrophilic treatment or a water repellency treatment from the viewpoint of stably supporting the oxygen-absorbing particles.

The coverage ratio of the surface of the carrier particles with oxygen-absorbing particles (the area covered by the oxygen-absorbing particles on the surface of the carrier particles / the total surface area of the carrier particles × 100 (unit (%))) is: Although it is set as appropriate according to the mass ratio, etc., it can be in the range of 2% to 80%.
In the present invention, when the average primary particle diameter of the carrier particles is larger than the wavelength in the visible light region, for example, larger than 800 nm, it is preferably in the range of 2% to 50%. It is preferable to be in the range of 2% to 30%. This is because the oxygen-absorbing material has high transparency when the covering ratio is within the above-described range.
In addition, as a measuring method of a coating ratio, it can determine by observation with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
Moreover, Hitachi S-4500 can be used as a scanning electron microscope, and Hitachi H-9000 can be used as a transmission electron microscope.

The light transmittance of the carrier particles is not particularly limited as long as desired transparency can be imparted to the oxygen-absorbing material, and can be 75% or more, and more preferably 85% or more. preferable. This is because, when the transmittance is within the above range, the oxygen-absorbing material has high transparency.
The upper limit of the light transmittance of the carrier particles is preferably as high as possible, but is usually 95% or less from the viewpoint of the degree of freedom of material selection.
The light transmittance of the carrier particles refers to the total light transmittance of the measurement film dispersed in the transparent thermoplastic resin so that the content of the carrier particles is 30% by mass.
Further, the total light transmittance can be measured according to JIS K7361-1 (a test method for the total light transmittance of a plastic-transparent material).

As a method for forming the measurement film, a method is used in which a resin composition in which 70 parts by mass of a transparent thermoplastic resin and 30 parts by mass of carrier particles are uniformly mixed is prepared and formed into a thickness of 100 μm. Can do.
Moreover, as a mixing method, the method etc. which stir while heating and melting a transparent thermoplastic resin using extruders, such as a TEM biaxial near-line extruder by Toshiba Machine, etc. can be used, for example.
Furthermore, as a film forming method, for example, a known film forming method such as an inflation film forming machine such as a Co-RI inflation manufacturing apparatus manufactured by Sumitomo Heavy Industries Modern Co., Ltd., an extrusion film forming machine, a melt film forming machine or the like may be used. it can.
As the transparent thermoplastic resin, the total light transmittance and haze of the transparent thermoplastic resin-only film formed by the same method as the measurement film forming method, except that no carrier particles are added, are, for example, 90 % And 0 can be used.
Specifically, a linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolue SP2020) can be used as the transparent thermoplastic resin.

  The haze of the carrier particles is 3 or less, preferably 2 or less. This is because if the haze is large, the light diffusibility of the material increases and the permeability of the material decreases. About haze (haze), it can obtain by measuring the film for a measurement used by the transmittance | permeability measurement of the light of a carrier particle by JISK7136 (how to obtain the haze of a plastic-transparent material).

2. Oxygen-absorbing particles The oxygen-absorbing particles are supported on the surface of the carrier particles and have a nano-order size.
The oxygen absorbing particles are metal or metal oxide particles having oxygen absorbability.

Here, that the oxygen-absorbing particles have a nano-order size means that the average primary particle size of the oxygen-absorbing particles has a nano-order size.
In the present invention, the average primary particle size of the oxygen-absorbing particles is preferably 500 nm or less, more preferably in the range of 0.1 nm to 500 nm, particularly in the range of 0.1 nm to 100 nm. It is preferable that it is especially in the range of 0.1 nm-50 nm. This is because the oxygen-absorbing material is highly transparent due to the average primary particle size.
The method for measuring the average primary particle size can be the same as that described in the section “1. Carrier particles”.

The constituent material of the oxygen-absorbing particles is a metal or metal oxide having oxygen absorptivity.
In the present invention, the constituent material is preferably a metal having oxygen absorptivity. This is because, when the constituent material of the oxygen absorbing particles is a metal, the oxygen absorbing particles often have excellent oxygen absorbability. In addition, since the metal has low light transmittance, the effect of obtaining a highly transparent oxygen-absorbing material can be more effectively exhibited by adopting a configuration in which the metal is supported on the carrier particles.

Any metal having oxygen absorptivity may be used as the metal.
Here, what has oxygen absorptivity can be combined with oxygen.
Examples of such an oxygen-absorbing metal include iron, manganese, platinum, aluminum, zinc, tin, magnesium, chromium, silicon, cerium, titanium, and copper. Among them, iron, aluminum In particular, iron is preferable. This is because, by using the metal, oxygen-absorbing particles having excellent oxygen absorptivity can be formed.
The metal particles include particles whose surfaces are oxidized.
Further, the metal particles may contain a mixture, an alloy, or a mixture of these oxides containing two or more of the above metals.

  The metal oxide having oxygen absorptivity is usually in an oxygen deficient state, and is preferably oxygen deficient iron oxide, aluminum oxide, zinc oxide, cerium oxide, titanium oxide, and copper oxide, for example. Of these, oxygen-deficient iron oxide and aluminum oxide are preferable, and oxygen-deficient iron oxide is particularly preferable. This is because the metal oxide can form, for example, oxygen-absorbing particles excellent in oxygen-absorbing property and is inexpensive.

The number of bonds of oxygen contained in the metal oxide to the metal is not limited as long as it does not satisfy the stoichiometric number, and can be, for example, 80% or less of the stoichiometric number. Or less, and particularly preferably 50% or less. This is because the metal oxide has excellent oxygen absorptivity due to the number of bonds.
Specifically, when iron oxide (III) (Fe ₂ O _y ) is used as the metal oxide, _y satisfying the stoichiometric number is 3, and the value of y is 2.4 or less. In particular, it is preferably 2, 1 or less, and particularly preferably 1.5 or less.

  Examples of a method for forming such an oxygen-deficient metal oxide include a method of extracting oxygen from a crystal lattice by reducing the metal oxide. For example, when the metal oxide is iron oxide, reduced iron obtained by reducing iron oxide can be used.

The types of the constituent materials are not limited to those using only one type, and two or more types may be used. When there are two or more kinds of constituent materials, for example, oxygen absorbing particles whose constituent material is iron and oxygen absorbing particles whose constituent material is iron oxide can be mixed and used.
When there are two or more types, oxygen absorbing particles formed from a mixture of both oxygen and iron oxide may be used as the oxygen absorbing particles.

  The oxygen-absorbing particles may have the same shape as the carrier particles as long as it can efficiently absorb oxygen.

  The structure of the oxygen-absorbing particles may be a porous structure having pores, but is usually a solid structure having no pores.

  The content ratio of the oxygen-absorbing particles to the carrier particles, that is, the mass ratio of oxygen-absorbing particles carried on one carrier particle (total mass of oxygen-absorbing particles carried on the carrier particles / mass of carrier particles × 100 ( The unit (%)) can be in the range of 1% to 30%, preferably in the range of 1% to 20%, in particular in the range of 1% to 10%. It is preferable that This is because, when the mass ratio is within the above range, the oxygen-absorbing material is excellent in oxygen-absorbing property.

3. Oxygen-absorbing material The light-transmitting rate of the oxygen-absorbing material of the present invention is not limited as long as it can form a highly transparent packaging material, for example, and can be 70% or more. % Or more is preferable. This is because, when the transmittance is within the above range, the oxygen-absorbing material has high transparency.
The upper limit of the light transmittance of the oxygen-absorbing material is preferably as high as possible, but is usually 95% or less from the viewpoint of the degree of freedom of material selection.
Further, the light transmittance of the oxygen-absorbing material is the same as the light transmittance of the carrier particles in the measurement film dispersed in the transparent thermoplastic resin so that the content of the oxygen-absorbing material is 30% by mass. This is the total light transmittance.
As a method for forming the measurement film, a method similar to the method described in the section “1. Carrier particles” can be used, and the measurement film is formed using an oxygen absorbing material instead of the carrier particles. Can be used.

The oxygen-absorbing material has carrier particles and oxygen-absorbing particles, but may have other configurations as necessary.
Examples of the other configuration include an oxygen-absorbing catalyst that is supported on at least one surface of the carrier particles and the oxygen-absorbing particles and catalyzes the expression of the oxygen-absorbing performance of the oxygen-absorbing particles.
Examples of the oxygen-absorbing catalyst include metal halides described in the section “B. Packaging material” described later.
As a method for supporting the oxygen absorbing catalyst on the surface of the carrier particles, the surface of the oxygen absorbing particles, etc., firstly, particles having oxygen absorbing particles supported on the surface of the carrier particles are prepared, and then an aqueous solution of metal halide or the like is sprayed. The method of doing can be mentioned.

  The method for producing the oxygen-absorbing material may be any method that allows oxygen-absorbing particles to be supported on the surface of carrier particles. For example, a particle preparation step for preparing carrier particles and oxygen-absorbing particles respectively, Examples thereof include a method having a firing step of firing a dispersion of both particles after preparing a uniformly dispersed dispersion and a grinding step of grinding the obtained fired product.

In the particle preparation step, the method for preparing the carrier particles and the oxygen-absorbing particles is not particularly limited as long as it is a method capable of forming particles having a desired particle diameter.
Examples of the formation method include a pulverization method, a gas phase synthesis method, a liquid phase synthesis method, an aerosol heating method, and a sol-gel method. Further, examples of the vapor deposition method include a PVD (physical vapor deposition) method and a CVD method (chemical vapor deposition method). In addition, conventionally known fine particles such as spray pyrolysis method, hot soap method, reverse micelle method, ultrasonic irradiation method, liquid phase reduction method, sol-gel method, high temperature high pressure (supercritical) hydrothermal synthesis method, etc. as liquid phase growth method A forming method can be used.
The average primary particle size of the carrier particles and oxygen-absorbing particles prepared in this step is, for example, the average primary particle size described in the above-mentioned sections “1. Carrier particles” and “2. Oxygen-absorbing particles”. The average primary particle diameter of each particle constituting the oxygen-absorbing material can be the same.

The mixture formed in the baking step may contain only the both particles, or a resin material or the like may be added as necessary.
As a method for preparing the above mixture, for example, when dispersing both particles, put the particles in a solution containing an appropriate dispersant or resin material, and obtain a uniform dispersion using a shaker, a bead mill or the like. The method can be used.
In addition, about the said dispersing agent and resin material, the general dispersing agent and resin material which are used for adhesion of the particles by baking can be used.
As the firing temperature and firing time of the mixture of both particles in the firing step, the surface of both particles is partially melted, and by forming an intermediate layer in which the constituent materials of both particles are mixed at the interface of both particles, It is sufficient if both particles can be fixed.
Specifically, in both particles, when the constituent material of the carrier particles is silicon oxide (SiO ₂ ) and the constituent material of the oxygen-absorbing particles is iron (Fe), the firing temperature is 400 ° C. to 1200 ° C. The firing time can be in the range of 0.5 to 48 hours.

As a method for pulverizing the calcined product in the pulverization step, any method can be used as long as the calcined product is pulverized into a particle state, that is, a state in which carrier particles are not bonded to each other through oxygen-absorbing particles. Good.
Examples of the pulverization method include a method in which the fired product is dispersed in an appropriate solvent, and mechanical dispersion or interfacial chemical dispersion is performed.
Examples of the mechanical dispersion method include an ultrasonic dispersion method, a method using a shear field, a method in which fired products collide and disperse at high speed, and a fired product at a contact point between high-speed moving media using beads or the like. And the like.
Examples of the interfacial scientific dispersion method include a method using charging, pH adjustment, a dispersion method using a surfactant, a chemical surface modification method for performing silane coupling treatment on the surface, and a method using a polymer coating. Can do.

In addition, as the production method, after preparing the carrier particles, the carrier particles are immersed in a solution containing an oxygen absorbing material (for example, an aqueous solution containing iron (II) chloride tetrahydrate or the like if iron-based), An example is a method in which the oxygen-absorbing material is supported on carrier particles using a chemical reaction.
Further, as the above production method, after preparing the carrier particles, a method of forming oxygen-absorbing particles directly on the surface of the carrier particles using a hydrothermal reaction or a supercritical reaction may be used.

4). Applications The oxygen-absorbing material of the present invention may be used as long as it requires oxygen absorption. For example, an oxygen-absorbing layer disposed in an inner layer of an oxygen-barrier layer of a packaging material that requires oxygen-barrier properties, Oxygen-absorbing layer for removing residual oxygen in packaging containers, oxygen-absorbing material for preventing the growth of aerobic microorganisms and insects, yellowing due to oxidation of sebum remaining on the fibers, oxygen for suppressing the growth of mold and other bacteria Absorbing materials, members for metal oxidation (corrosion), and the like can be mentioned.

B. Next, the packaging material of the present invention will be described.
The packaging material of the present invention includes a barrier layer and an oxygen absorbing layer that is disposed on one surface of the barrier layer and contains an oxygen absorbing material. The oxygen absorbing material includes carrier particles and the carrier particles. And oxygen-absorbing particles having a nano-order size, and the carrier particles are particles of at least one oxide, nitride, or oxynitride of metal and silicon, and the oxygen-absorbing particles The particle is a metal or metal oxide particle having oxygen absorptivity.

Such a packaging material of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the packaging material of the present invention. As illustrated in FIG. 1, the packaging material of the present invention has a barrier layer 1 and an oxygen absorption layer 2 disposed on one surface of the barrier layer 1 and containing an oxygen absorption material. The absorbent material has carrier particles and oxygen-absorbing particles supported on the surface of the carrier particles and having a nano-order size, and the carrier particles include at least one oxide of metal and silicon, nitride, or Oxynitride particles, wherein the oxygen absorbing particles are metal or metal oxide particles having oxygen absorbability.
In this example, the packaging material has a barrier layer 1, an adhesive layer 3, and a sealant layer 4, and the oxygen absorbing layer 2 is an adhesive layer 3.

  According to the present invention, since the oxygen absorbing layer contains the above-described oxygen absorbing material, the packaging material of the present invention has high transparency and reduced odor generation.

The packaging material of the present invention has a barrier layer and an oxygen absorbing layer.
Hereinafter, each structure of the packaging material of this invention is demonstrated in detail.

1. Location of Oxygen Absorbing Layer The packaging material of the present invention has at least a barrier layer and an oxygen absorbing layer.
As a layer configuration of such a packaging material, in addition to the barrier layer and the oxygen absorbing layer, the packaging material may have an inner surface layer disposed on one surface of the barrier layer described in “4. Good.
Here, when the layer configuration includes an inner surface layer, the oxygen absorbing layer may be disposed as an oxygen absorbing coating layer having only an oxygen absorbing function, but is disposed integrally with the inner surface layer. In other words, the oxygen absorbing layer may be disposed as the inner surface layer.
In the present invention, it is particularly preferable that the oxygen absorbing layer is disposed as an inner surface layer. This is because the oxygen absorbing layer is disposed as the inner surface layer, so that the packaging material can have a small number of constituent layers and can be easily formed.
FIG. 1 already described shows an example in which the oxygen absorption layer 2 is disposed as an inner surface layer.

When the oxygen absorbing layer is disposed as an inner surface layer, the oxygen absorbing layer may be disposed as any layer included in the inner surface layer. However, when the inner surface layer includes an adhesive layer that adheres two layers, the adhesive layer It is preferable to arrange as
For example, the layer structure of the packaging material has an adhesive layer and a sealant layer in this order as an inner surface layer on one side of the barrier layer, a support substrate that supports the barrier layer, an adhesive layer, and a sealant layer In this order, the oxygen-absorbing layer can be arranged as any layer of the inner surface layer, but is preferably arranged as an adhesive layer.
The adhesive layer can be easily formed after the shipment order, that is, immediately before the production of the packaging material. For example, as a method for producing the packaging material of the present invention, a barrier layer and a sealant layer are prepared in advance, and after shipping order, an adhesive stored in a state not in contact with oxygen is provided between the two prepared layers. The manufacturing method etc. which apply | coat and form the adhesive bond layer which adhere | attaches both layers can be used. Therefore, when the oxygen absorbing layer is arranged as an adhesive layer, the oxygen absorbing layer can be prevented from absorbing oxygen before the packaging material wraps the contents.
Note that FIG. 1 already described shows an example in which the adhesive layer 3 and the sealant layer 4 are provided as the inner surface layer, and the oxygen absorbing layer 2 is disposed as the adhesive layer 3.
2A shows an example in which only the sealant layer 4 is provided as the inner surface layer, and the oxygen absorbing layer 2 is disposed as the sealant layer 4. FIG. 2B shows the support base material as the inner surface layer. 5 shows an example in which the adhesive layer 3 and the sealant layer 4 are provided, and the oxygen absorbing layer 2 is disposed as the adhesive layer 3.

When the oxygen-absorbing layer is used as an oxygen-absorbing coating layer, the oxygen-absorbing layer may be disposed on one surface of the barrier layer, for example, a portion in contact with the surface of the barrier layer, a barrier of the supporting substrate It can be a part in contact with the surface opposite to the layer, a part sandwiched between the adhesive layer and the sealant layer, or the like.
Here, in FIG. 3, the packaging material 10 includes the support base 5, the adhesive layer 3, and the sealant layer 4 as the inner surface layer, and the oxygen absorption layer 2 as the oxygen-absorbing coating layer. An example in which 2 is arranged between the adhesive layer 3 and the sealant layer 4 is shown.

2. Oxygen Absorbing Layer The oxygen absorbing layer in the present invention is a layer that is disposed on one surface of the barrier layer and contains an oxygen absorbing material.
Here, the one surface of the barrier layer refers to the surface on the side where the contents of the barrier layer are enclosed when the package is formed using the packaging material.

(1) Constituent material The oxygen absorbing layer contains an oxygen absorbing material.
Such an oxygen-absorbing material can be the same as the contents described in the section “A. Oxygen-absorbing material”, and thus the description thereof is omitted here.

  The content of the oxygen-absorbing material in the oxygen-absorbing layer is not particularly limited as long as it can provide a desired oxygen-absorbing performance, and can be within a range of 3% by mass to 80% by mass. It is preferable to be in the range of mass%, and it is particularly preferable to be in the range of 3% to 30% by mass. This is because, when the content is within the above range, the oxygen absorbing layer has excellent oxygen absorptivity.

The oxygen absorbing layer usually has a binder resin that disperses and holds an oxygen absorbing material or the like.
As such a binder resin, when the oxygen absorption layer is disposed as an inner surface layer, the constituent material of each inner surface layer described in “4. Inner surface layer” described later can be used.
When the oxygen absorbing layer is included as an oxygen absorbing coating layer, examples of the binder resin include a thermoplastic resin, a cured product of a light or electron beam curable resin, a cured product of a thermosetting resin, and a cured sol-gel material. A thing etc. can be used. In the present invention, it is preferable that the binder resin is a thermoplastic resin. This is because the oxygen absorption layer can be easily formed by using the binder resin.
Examples of the thermoplastic resin include polyethylene resins, polypropylene resins, polystyrene resins, vinyl resins such as polyvinyl chloride, polyester resins, and polyamide resins. Further, only one type of thermoplastic resin may be used, but two or more types may be used in combination. In the present invention, it is particularly preferable that the thermoplastic resin is a polyethylene resin or a polypropylene resin.
As the light or electron beam curable resin, for example, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin compound comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which an oligomer such as polyester acrylate and polyether acrylate is dissolved in a polyfunctional acrylate monomer. Further, only one type of light or electron beam curable resin may be used, but two or more types may be used in combination.
Examples of the cured product of the thermosetting resin include polymethyl methacrylate, polyacrylate, polycarbonate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile, and a mixture of styrene copolymers. , Poly (-4-methylpentene-1), phenol resin, epoxy resin, cyanate resin, maleimide resin, polyimide resin, and the like. Also, those modified with polyvinyl butyral, acrylonitrile-butadiene rubber, polyfunctional acrylate compounds, etc., crosslinked polyethylene resins, mixtures of crosslinked polyethylene and epoxy resins, mixtures of crosslinked polyethylene and cyanate resins, polyphenylene ethers and epoxy resins Examples thereof include a thermosetting resin modified with a thermoplastic resin such as a mixture, a mixture of polyphenylene ether and cyanate resin. Moreover, although the said thermosetting resin may use only 1 type, you may use 2 or more types together.
As the cured product of the sol-gel material, for example, as disclosed in Japanese Patent No. 2556940, a composition containing an alkoxysilane, a silane coupling agent, and polyvinyl alcohol is formed by polycondensation by a sol-gel method. Can do. Further, as disclosed in Japanese Patent No. 3387814, it can be formed by hydrolysis condensation using an alkoxysilane and an amino group-containing organic compound or (meth) acrylic polymer.

From the viewpoint of improving the light transmittance of the oxygen absorbing layer, the binder resin preferably has a small refractive index with respect to the carrier particles in the oxygen absorbing material. In particular, it is more effective when the carrier particles are larger than the nano-order size.
The difference in refractive index between the binder resin and the carrier particles is, for example, preferably 0.5 or less, and more preferably 0.2 or less. This is because when the refractive index difference is in the above-described range, interface reflection of light is reduced, and the oxygen absorption layer has high transparency.
The refractive index of the binder resin can be measured using an Abbe refractometer (JIS K 7142: 2009 (plastic-refractive index calculation method)), a spectroscopic ellipsometer, a reflectance measurement method, or the like. The refractive index of the carrier particles can be measured by an Abbe refractometer or a method using a V block prism using a refracting liquid (contact liquid) (Kalnew precision refractometer; Shimadzu Corporation).

The oxygen-absorbing layer may include an oxygen-absorbing catalyst that catalyzes oxygen absorption from the viewpoint of efficiently performing oxygen absorption by the oxygen-absorbing material, if necessary.
Examples of the oxygen absorbing catalyst include sodium chloride (NaCl), sodium fluoride (NaF), sodium bromide (NaF) when the constituent material of the oxygen absorbing particles is iron, aluminum, titanium, cerium, zinc, or the like. Examples thereof include metal halides such as NaBr), potassium chloride (KCl), potassium fluoride (KF), and potassium bromide (KBr).
In addition, the content of the oxygen absorption catalyst can be appropriately set according to the use of the oxygen absorption layer, and the range is, for example, from 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the oxygen absorption material. Can be inside.

The oxygen absorbing layer may have an additive as necessary within a range that does not impair the oxygen absorbing property, transparency, and the like of the oxygen absorbing layer.
As said additive, the well-known additive used for packaging materials, such as a plasticizer, an antistatic agent, and a coloring material, can be mentioned.
Moreover, about content of the said additive, it can set suitably according to the kind etc. of additive.

(2) Others The thickness of the oxygen-absorbing layer is not limited as long as an oxygen-absorbing layer having a desired oxygen-absorbing property can be formed, and can be in the range of 1 μm to 120 μm, in particular, 3 μm to 80 μm. It is preferable to be within the range. This is because, when the thickness is within the above range, the oxygen absorbing layer has excellent oxygen absorptivity.

The light transmittance of the oxygen absorbing layer is not particularly limited as long as it exhibits desired transparency, and can be, for example, 70% or more, preferably 80% or more, and particularly 85%. The above is preferable. It is because the packaging material of this invention becomes a highly transparent thing because the transmittance | permeability of the said light is the above-mentioned range.
The light transmittance of the oxygen absorbing layer refers to the total light transmittance of the oxygen absorbing layer.

The haze of the oxygen absorption layer can be set to 3 or less, for example, preferably 2 or less, and particularly preferably 1 or less. It is because the packaging material of this invention becomes a highly transparent thing because the said haze is the above-mentioned range.
The haze of the oxygen absorbing layer can be measured according to JIS K7361-1 (Plastic—How to determine haze of transparent material).

As a method for forming the oxygen absorbing layer, any method capable of forming an oxygen absorbing layer having a desired thickness may be used.
Examples of the forming method include a method in which, when the binder resin is a thermoplastic resin, the constituent materials are heated and melted to form a desired shape.
Examples of the film forming method include an extrusion method such as a T-die and an inflation method.
In addition, as the above-described forming method, an oxygen absorbing layer forming composition is formed by using a composition containing a solvent capable of dispersing or dissolving the constituent materials and applying the oxygen absorbing layer forming composition. A method can be mentioned. Moreover, the said formation method shall perform the process which dry-removes a solvent from the coating film of the said composition for oxygen absorption layer formation, a hardening process, etc. as needed.
Examples of the coating method include known coating methods such as roll coating, gravure coating, and kiss coating. As said hardening process, it changes according to the said binder resin, and when the binder resin is a thermosetting resin, the method of heating can be mentioned.

3. Barrier layer The barrier layer in the present invention has an oxygen barrier property.

Here, the oxygen permeability (23 ° C., 65% RH) of the barrier layer is not particularly limited as long as a packaging material having a desired oxygen barrier property can be obtained. For example, 0.5 cc · m ⁻² · day ^{− 1} · atm ⁻¹ or less.
The oxygen permeability can be obtained according to JIS K 7126.

The oxygen barrier layer may be a resin layer, a metal or metal oxide vapor deposition layer, a metal foil layer, or the like.
In the present invention, from the viewpoint of making the packaging material highly transparent, the type is preferably a resin layer or a metal oxide deposition layer.
The resin material constituting the resin layer is not particularly limited as long as it can provide a desired oxygen barrier property. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer described in International Publication No. 2015/046485 and the like. Can be mentioned.
As a metal oxide which comprises the said vapor deposition layer, what is necessary is just to be able to provide desired oxygen barrier property, For example, the silicon oxide, aluminum oxide, etc. which are described in international publication 2015/046485 etc. can be mentioned. .
As a metal which comprises the said vapor deposition layer, what is necessary is just to be able to provide desired oxygen barrier property, For example, the silicon | silicone, aluminum, etc. which are described in Unexamined-Japanese-Patent No. 2015-208867 can be mentioned.
As a metal which comprises the said metal foil layer, the aluminum as described in international publication 2015/046485 etc. can be mentioned, for example.
Moreover, as the oxygen barrier layer, a layer in which a gas barrier coating film is further provided on the vapor deposition layer can be used. In addition, as a gas barrier coating film, the thing as described in Unexamined-Japanese-Patent No. 2012-35516, international publication 2015/046485 etc. can be used, for example.

The thickness of the oxygen barrier layer is set according to the desired oxygen barrier property.
Such a thickness varies depending on the type of the oxygen barrier layer. For example, when the type is a resin layer, the thickness can be in a range of 10 μm to 30 μm.
Moreover, when the said kind is a vapor deposition layer, it can be in the range of 50 to 4000 tons.
Furthermore, when the said kind is a metal foil layer, it can be in the range of 5 micrometers-20 micrometers.

  As the formation method of the oxygen barrier layer, a known formation method corresponding to the type of the oxygen barrier layer can be used.

4). Inner surface layer Although the packaging material of this invention has a barrier layer and an oxygen absorption layer at least, it may have an inner surface layer arrange | positioned at one surface of a barrier layer as needed.
As such an inner surface layer, any material may be used as long as it is disposed on one surface of the barrier layer and is included in the package when the package is formed. For example, the sealant layer and the barrier layer used for forming the package are supported. Examples thereof include a supporting substrate to be bonded, an adhesive layer for bonding two layers, and the like.
In the present invention, the inner surface layer usually includes a sealant layer. This is because, when the sealant layer is included as the inner surface layer, the packaging material of the present invention makes it easy to manufacture the package.
Moreover, in this invention, it is preferable that the said inner surface layer is what has an adhesive bond layer. By having the adhesive layer, other layers other than the adhesive layer are prepared in advance, and the layer configuration and the like can be flexibly adjusted according to the contents of the shipping order.
For example, a barrier layer and a sealant layer are prepared in advance, and after shipping order, an adhesive is applied between the two layers prepared in advance to form an adhesive layer that adheres both layers. This is because the packaging material of the contents of the shipping order can be easily manufactured.

(1) Sealant layer The sealant layer is used for forming a package.
Here, as for what is used for formation of a package, for example, two packaging materials are arranged so that the sealant layers face each other and overlap each other, and the sealant layers arranged so as to face each other by heating the peripheral end portions. Can be melted and fused together to be used for forming the seal portion.
Moreover, since it is used for formation of a package, the sealant layer is usually disposed on the outermost surface of the inner surface layer.

  As a constituent material of such a sealant layer, a material generally used for a sealant layer of a packaging material can be used. For example, a polyolefin system having a heat seal property described in International Publication No. 2015/046485 Resin or the like can be used.

  When the sealant layer is not used as an oxygen absorbing layer, the thickness of the sealant layer may be, for example, any adhesive that can form a packaging container having a desired strength, and is within a range of 10 μm to 200 μm. be able to.

As a method for forming the sealant layer, a known method such as a method described in International Publication No. 2015/046485 can be used.
Specifically, the formation method can be the same as that described in the section “2. Oxygen absorption layer”.

(2) Adhesive layer The said adhesive layer adheres two layers.
The two layers bonded by such an adhesive layer may be any layer other than the adhesive layer, such as an oxygen absorbing layer as an oxygen absorbing coating layer, a barrier layer, and a supporting substrate. Or between a sealant layer, between a barrier layer and a support base material or a sealant layer, between a support base material and a sealant layer, etc. can be mentioned.
Moreover, an adhesive bond layer is normally used for adhesion | attachment of two layers prepared beforehand.

The constituent material of the adhesive layer may be an adhesive that can bond the members arranged on both sides of the adhesive layer with a desired strength, for example, a thermosetting adhesive, an ultraviolet curable adhesive, A cured product such as an electron beam curable adhesive can be used.
As the adhesive, a solidified hot melt adhesive, a pressure sensitive adhesive, or the like can also be used.

  Specific examples of the thermosetting adhesive, ultraviolet curable adhesive, and electron beam curable adhesive include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, and polyacrylic acid. Copolymerization of polyacrylic acid adhesive, cyanoacrylate adhesive, ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid Ethylene copolymer adhesive, cellulose adhesive, polyurethane adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, polyolefin adhesive, urea resin, melamine resin, etc. Adhesive, phenolic resin adhesive, epoxy adhesive, reactive (meth) acrylic adhesive, black Purengomu, nitrile rubber, styrene - butadiene made of rubber or the like elastomeric adhesive, a silicone adhesive, an alkali metal silicate, inorganic adhesive or the like made of a low-melting glass. In addition, you may use these adhesive agents in mixture of 2 or more types as needed.

Examples of the hot-melt adhesive include thermoplastic resins such as polyvinyl acetate resin described in JP-A-11-170791.
Two or more kinds of the above thermoplastic resins may be mixed and used as necessary.

Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, and synthetic rubber-based pressure-sensitive adhesives.
Two or more kinds of the pressure-sensitive adhesives may be mixed and used as necessary.

The thickness of the adhesive layer is not particularly limited as long as the members arranged on both sides of the adhesive layer can be bonded to each other with a desired strength. For example, the coating amount in a dry state is 0.1 g / m. ^2-10. It can be in the range of g / m ² .

As a method for forming the adhesive layer, for example, a known forming method described in International Publication No. 2015/046485 can be used.
Specifically, the formation method can be the same as that described in the section “2. Oxygen absorption layer”.

(3) Support base material The said support base material supports a barrier layer, and is used especially when using a vapor deposition layer as a barrier layer.
Moreover, since it is used for support of a barrier layer, a support base material is normally arrange | positioned so that a barrier layer may be contact | connected.

As a constituent material of such a support base material, any material can be used as long as it can stably support the barrier layer. For example, resin materials such as polyester resins and polypropylene resins described in International Publication No. 2015/046485 Can be used.
When the support substrate is not used as the oxygen absorbing layer, the thickness of the support substrate may be any as long as it can stably support the barrier layer, and can be, for example, in the range of 6 μm to 100 μm.

  The method for forming the support substrate may be any method that can obtain a support substrate having a desired thickness. For example, the same method as described in the above section “2. Oxygen absorption layer” may be used. it can.

5. Other Layers The packaging material of the present invention may have other layers in addition to the barrier layer, the oxygen absorbing layer, and the inner surface layer.
Examples of such other layers include a gas barrier release layer that is disposed on the surface of the sealant layer opposite to the barrier layer and is peeled and removed when the package is formed.
As said gas-barrier peeling layer, the thing as described in international publication 2015/046485 etc. can be mentioned, for example.

6). Packaging material The light transmittance of the packaging material of the present invention is not particularly limited as long as it exhibits desired transparency, and can be, for example, 70% or more, preferably 80% or more. It is preferably 85% or more. It is because the packaging material of this invention becomes a highly transparent thing because the transmittance | permeability of the said light is the above-mentioned range.
The light transmittance is the total light transmittance of the packaging material.

  As a haze of the said packaging material, it can be set to 3 or less, for example, it is preferable that it is 2 or less especially, and it is especially preferable that it is 1 or less. It is because the packaging material of this invention becomes a highly transparent thing because the said haze is the above-mentioned range.

As a method for producing the packaging material of the present invention, any method can be used as long as the above-described components can be accurately laminated. For example, a preparatory step for preparing a layer other than the oxygen-absorbing layer in advance, And an oxygen absorbing layer forming step of forming an oxygen absorbing layer by applying an oxygen absorbing layer forming composition on the surface.
More specifically, when the layer structure of the packaging material is a layer structure in which a barrier layer, a support substrate, an oxygen absorption layer as an adhesive layer, and a sealant layer are laminated in this order, the support substrate and the support A barrier laminate including a barrier layer formed on a substrate and a sealant layer are prepared, and after shipping order, an oxygen absorbing layer forming composition is applied between the barrier laminate and the sealant layer. The method of arrange | positioning the oxygen absorption layer as an adhesive bond layer can be mentioned.
Further, when the above layer configuration is a layer configuration in which the barrier layer, the support base material, and the oxygen absorbing layer as the sealant layer are laminated in this order, a barrier laminate is prepared, and after the shipment order, the barrier laminate The method of arrange | positioning the oxygen absorption layer as a sealant layer by coating the composition for oxygen absorption layer formation on the surface of the support base material contained in a body can be mentioned.

  In addition, when the layer configuration is a layer configuration in which a barrier layer, a support base, an adhesive layer, an oxygen-absorbing coating layer, and a sealant layer are stacked in this order, the manufacturing method includes a barrier laminate. And a sealant layer having an oxygen-absorbing coating layer formed on the surface, and after the shipment order, the barrier laminate and the sealant layer are arranged so that the supporting substrate and the oxygen-absorbing coating layer face each other, A method of adhering between both layers with an adhesive layer may be used.

As a method for forming a package using the packaging material of the present invention, for example, known methods described in JP-A Nos. 2002-192646 and 2012-35516 can be used.
Specifically, in the case where a sealant layer is provided as a packaging material, the above-described forming method is performed by arranging two packaging materials so that the sealant layers of the respective packaging materials face each other, It is possible to use a method in which the sealant layer is formed by melting and fusing the sealant layers arranged opposite to each other by heating.
Further, when the sealant layer is not provided as the packaging material, the forming method can be a method of bonding the peripheral end portions of the two packaging materials using a separately prepared adhesive.

7). Applications The packaging material of the present invention may be used as long as it is used for forming a package requiring transparency and oxygen absorption in the inner layer of the oxygen barrier layer.
Examples of the use of such a package include packaging use for contents that cause quality deterioration due to the presence of oxygen, such as foods, pharmaceuticals, industrial materials, batteries such as lithium ion batteries, electronic devices, and electronic parts. be able to.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
(1) Preparation of Oxygen Absorbing Material Spherical silica particles (Toagosei Co., Ltd. HPS-3500 (average particle size 3.5 μm)) were prepared as carrier particles.
Next, as oxygen-absorbing particles, iron-absorbing iron particles were produced by a direct reduction method.
Specifically, first, iron (II) chloride tetrahydrate (FeCl ₂ .4H ₂ O; Wako Pure Chemical Industries, Ltd.) 0.92 mmol, sodium hydroxide (NaOH; Wako Pure Chemical Industries, Ltd.) 0. 92 mmol was dissolved in 450 mL of ion exchange water. The solution was transferred to a three-necked flask, stirred while flowing N ₂ gas, and cooled in an ice bath to adjust the temperature of the solution to 5 ° C.
Thereafter, 0.5 mmol of NaOH and 17.6 mmol of sodium borohydride (NaBH ₄ ; Wako Pure Chemical Industries, Ltd.) are dissolved in 50 ml of ion-exchanged water, and the solution is put into a stirring three-necked flask to thereby precipitate iron particles. Obtained.
The precipitate was washed with ion-exchanged water and ethanol to obtain iron particles. When the particle size of the particles was measured by SEM, the average primary particle size of 100 particles was 52 nm.
Next, 65 parts by mass of spherical silica particles as carrier particles and 35 parts by mass of iron particles as oxygen-absorbing particles were uniformly mixed, and after heat treatment at 600 ° C. for 3 hours in a nitrogen atmosphere, acetic acid was used. It was dissolved in a mixed solution of ethyl (Wako Pure Chemical Industries) and PGME (propylene glycol monomethyl ether; Showa Denko) 8: 2.
Thereafter, the solution was shaken with zirconia beads 2 mmφ for 1 hour, and then further shaken with 0.1 mmφ zirconia beads for 2 hours to prepare a uniformly dispersed oxygen-absorbing material (silica-supported iron particles) solution.

(2) Preparation of adhesive composition The adhesive composition was prepared with the following formulation.

(Blend ratio of adhesive composition)
・ Oxygen-absorbing material: 43 parts by mass of the above-described oxygen-absorbing material (silica-supported iron particles) ・ Adhesive (main agent): 54 parts by mass of polyester resin (manufactured by Rock Paint, trade name: RU-004) ): Aliphatic polyisocyanate (manufactured by Rock Paint, trade name: H-1) 3 parts by mass / dispersing agent: 21.5 parts by mass of alkyl ammonium salt polymer (50 parts by mass with respect to 100 parts by mass of the oxygen-absorbing material)
・ Oxygen absorption start catalyst: 4.3 parts by mass of sodium chloride (10 parts by mass with respect to 100 parts by mass of oxygen absorbing material)
・ Solvent: ethyl acetate (amount in which the ratio of all solids other than the solvent is 25% by mass)

(3) Production of Oxygen Absorbing Barrier Film A transparent barrier PET (polyethylene terephthalate) film (thickness 12 μm, large) in which a silicon-based barrier layer is formed on the surface of a PET film as a supporting base material It applied so that the dry application quantity might be set to 9g +/- 1g / m < ² > using the Mayer bar on the PET base material side surface of Nippon Printing Co., Ltd. brand name IB-PET-PIR). A coating film of the adhesive composition was prepared by drying at 70 ° C. for 30 seconds.
The film coated with this adhesive composition is subjected to lamination by thermocompression bonding at 80 ° C. using a linear low-density polyethylene (LLDPE) film (thickness 50 μm, Phutamura Chemical Co., Ltd., XMTN) and a roller, By performing heat aging treatment in the atmosphere at 40 ° C. for 3 days, the transparent barrier PET film (barrier layer and supporting substrate (PET)), adhesive layer (cured material layer of the above adhesive composition), and LLDPE are in this order. Thus, an oxygen-absorbing barrier film having a thickness of 70 μm was obtained.

(4) Evaluation of oxygen-absorbing barrier film The obtained oxygen-absorbing barrier film was evaluated for total light transmittance, haze, oxygen-absorbing property, and packaging form suitability.

(A) Total light transmittance and haze The total light transmittance and haze of the oxygen-absorbing barrier film were measured with a haze meter (trade name: HM-150, manufactured by Murakami Color Research Laboratory).
As a result, the total light transmittance was 85%, and the haze was 3, indicating good transparency.

(B) Oxygen absorption The oxygen absorption barrier film was cut into 100 cm ² and hermetically sealed in a lidded glass bottle (volume 106 cc) together with 15 cc of distilled water. At this time, a sensor chip (PreSens, SP-PSt3-NAU-D5) for measuring oxygen concentration was fixed to the wall surface of the glass bottle in the glass bottle with an adhesive in a direction that can be measured by the sensor from the outside of the glass bottle.
Then, the oxygen concentration in the glass bottle after 720 hours has been measured using an oxygen concentration meter (PreSens, Fixbox 3), and the residual oxygen amount is calculated by converting the actual oxygen volume from the initial volume of the glass bottle. The amount absorbed was determined. It was found that the oxygen absorption amount after 720 hours after sealing was a sufficient oxygen absorption amount of 15 cc / 100 cm ² .
The oxygen absorption performance was judged to be sufficient if it was 10 cc / 100 cm ² or more.

(C) Packaging material form evaluation Using two oxygen-absorbing barrier films, the contents were filled with cut rice cake (Sato Foods Co., Ltd., sugar cut rice 50 g / piece), and heat sealed to 60 mm x 110 mm x 23 mm. Then, a pouch was prepared by heat-sealing the remaining one side, and a storage test was performed at room temperature (N = 5). As a result, even after storage for 30 days, all the samples have no appearance change such as the occurrence of color and mold on the cut straw, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. It was confirmed that the packaging material was suitable for storage.

[Example 2]
An oxygen-absorbing barrier film was prepared in the same manner as in Example 1 except that Sigma-Aldrich Nanopowder (product number: 746835, average particle size 25 nm) was used instead of the oxygen-absorbing particles (iron particles) prepared in Example 1. Evaluation was performed.
As a result, the total light transmittance was 91%, and the haze was 0, indicating good transparency.
Further, the oxygen absorption amount was 30 cc / 100 cm ^2, and it was confirmed that the oxygen absorption was good.
Furthermore, in the samples after 30 days storage, there is no change in appearance such as color or mold on the cut straw, no change in texture, no change in appearance such as discoloration or peeling of the pouch itself, and packaging material It was confirmed that it was suitable for storage.

[Comparative Example 1]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that the adhesive composition having the following blending ratio was used without adding the oxygen-absorbing material prepared in Example 1.
As a result, the total light transmittance was 91%, and the haze was 0, indicating good transparency.
Further, the oxygen absorption amount was 0 cc / 100 cm ^2, and it was confirmed that there was no oxygen absorption.
Furthermore, in the sample after 30 days storage, the occurrence of mold was confirmed on the surfaces of all the bags, and it was found that the packaging material storage suitability was not sufficient.

(Blend ratio of adhesive composition)
-Adhesive (main agent): polyester resin (manufactured by Rock Paint, trade name: RU-004) 89 parts by mass-Adhesive (curing agent): aliphatic polyisocyanate (manufactured by Rock Paint, trade name: H-1 ) 11 parts by mass / solvent: Methyl acetate (amount in which the proportion of all solids other than the solvent is 16% by mass)

[Comparative Example 2]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that micro-order iron particles having an average particle diameter of 1 μm prepared by a pulverization method were used as oxygen-absorbing particles.
As a result, the total light transmittance was 50%, the haze was 15, and transparency was not obtained.
It was also found that the oxygen absorption amount was 10 cc / 100 cm ² and was a sufficient oxygen absorption amount.
Further, in the sample after 30 days storage, no change in the appearance of the surface of all candy and generation of mold were confirmed, and the packaging material storage suitability was sufficient.

[Example 3]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that Sigma-Aldrich nanoparticles (product number: 746878, average particle size 70 nm) were used as oxygen-absorbing particles (iron particles).
As a result, the total light transmittance was 90%, and the haze was 1, indicating good transparency.
Further, it was confirmed that the oxygen absorption was good at 20 cc / 100 cm ² .
Furthermore, in the samples after 30 days storage, there is no change in appearance such as color or mold on the cut straw, no change in texture, no change in appearance such as discoloration or peeling of the pouch itself, and packaging material It was confirmed that it was suitable for storage.

[Example 4]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that Toagosei Co., Ltd. HPS-0500 (average particle size: 0.75 μm) was used as the carrier particles (spherical silica particles).
As a result, the total light transmittance was 90%, and the haze was 1, indicating good transparency.
It was also found that the oxygen absorption amount was 20 cc / 100 cm ² and was a sufficient oxygen absorption amount.
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Example 5]
As the carrier particles (spherical silica particles), an oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that Ube Eximo High Precisiona FR (product number N2N, average particle size 0.2 μm) was used.
As a result, the total light transmittance was 91%, and the haze was 0, indicating good transparency.
Further, it was found that the oxygen absorption amount was a sufficient oxygen absorption amount of 23 cc / 100 cm ² .
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Example 6]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that DENKA spherical alumina (product number DAM03, average particle size 6.0 μm) was used as the carrier particles.
As a result, the total light transmittance was 87%, and the haze was 2, indicating good transparency.
Further, it was found that the oxygen absorption amount was 14 cc / 100 cm2, which was a sufficient oxygen absorption amount.
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Example 7]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 2 except that Ishihara Sangyo Co., Ltd. titanium oxide material (product number TTO-S-1, average particle size 0.08 μm) was used as the carrier particles.
As a result, the total light transmittance was 90%, and the haze was 0, indicating good transparency.
Further, it was found that the oxygen absorption amount was 22 cc / 100 cm 2 and the oxygen absorption amount was sufficient.
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Example 8]
70 parts by mass of linear low-density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolu SP2020), and 30 parts by mass of oxygen-absorbing particles (iron particles) produced in Example 1 A uniformly mixed master batch was prepared, and an oxygen-absorbing material-added sealant film having a thickness of 100 μm was prepared using a lab inflation film forming machine.
Next, an adhesive composition having the following blending ratio was applied to a transparent barrier PET (polyethylene terephthalate) film (thickness 12 μm, manufactured by Dai Nippon Printing Co., Ltd., trade name IB-PET-PIR) on the PET substrate side surface with a Meyer bar. It was applied so that the dry coating amount was 9 g ± 1 g / m ² . Next, a coating film of the adhesive composition was prepared by drying at 70 ° C. for 30 seconds.
The film coated with this adhesive composition is laminated by heat-pressing at 80 ° C. using the above-mentioned oxygen absorbing material-added sealant film and roller, and then subjected to heat aging treatment in the atmosphere at 40 ° C. for 3 days. Thus, an oxygen-absorbing barrier film in which a transparent barrier PET film (barrier layer and supporting substrate (PET)), an adhesive layer, and an oxygen-absorbing material-added sealant film were laminated in this order was obtained.

(Blend ratio of adhesive composition)
-Adhesive (main agent): polyester resin (manufactured by Rock Paint, trade name: RU-004) 89 parts by mass-Adhesive (curing agent): aliphatic polyisocyanate (manufactured by Rock Paint, trade name: H-1 ) 11 parts by mass / solvent: Methyl acetate (amount in which the proportion of all solids other than the solvent is 16% by mass)

When the obtained oxygen-absorbing barrier film was evaluated in the same manner as in Example 1, the total light transmittance was 90% and the haze was 1, indicating good transparency.
Further, it was found that the oxygen absorption amount was 13 cc / 100 cm ² and there was sufficient oxygen absorption performance.
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Comparative Example 3]
A sealant film having a thickness of 100 μm was formed with a lab inflation film forming machine using only a linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolu SP2020) without adding an oxygen absorbing material. A sample was prepared and evaluated in the same manner as in Example 8 except that the film was formed.

As a result, the oxygen-absorbing barrier film showed good transparency with a total light transmittance of 90% and a haze of 0.
The oxygen absorption amount was also 0 cc / 100 cm ² , confirming that there was no oxygen absorption. Furthermore, in the sample after 30 days storage, the occurrence of mold was confirmed on the surfaces of all the bags, and it was found that the packaging material storage suitability was not sufficient.

[Example 9]
In the same manner as in Example 1, an oxygen absorbing material (silica-supported iron particles) solution was prepared.
Next, a solution prepared so as to be 20 parts by mass of tetraethoxysilane, 1 part by mass of nitric acid, 9 parts by mass of pure water, 10 parts by mass of ethanol, and 15 parts by mass of the oxygen absorbing material was added to 100 g of a solution stirred for 5 hours. A polyvinyl alcohol aqueous solution adjusted to 100% by weight was added and stirred for 3 hours to prepare a sol solution as a coating liquid for coating to form an oxygen-absorbing coating layer.

  Moreover, after spin-coating the said sol solution on the PET base material side surface of transparent barrier PET (polyethylene terephthalate) film (thickness 12 micrometers, Dai Nippon Printing Co., Ltd. make, brand name IB-PET-PIR), at 70 degreeC. It dried for 1 hour and produced the laminated body by which the oxygen absorption coating layer with a coating film of 2 micrometers was laminated | stacked.

Next, an adhesive composition having the following blending ratio was applied to the surface of the oxygen-absorbing coating layer of the laminate using a Meyer bar so that the dry coating amount was 9 g ± 1 g / m ² . Next, a coating film of the adhesive composition was prepared by drying at 70 ° C. for 30 seconds.
The film coated with this adhesive composition is subjected to lamination by thermocompression bonding at 80 ° C. using a linear low-density polyethylene (LLDPE) film (thickness 50 μm, Phutamura Chemical Co., Ltd., XMTN) and a roller, Transparent barrier PET (barrier layer and supporting substrate (PET)), oxygen-absorbing coating layer, adhesive layer and sealant layer (LLDPE) are laminated in this order by performing heat aging treatment in the atmosphere at 40 ° C for 3 days. An oxygen-absorbing barrier film was prepared.

(Blend ratio of adhesive composition)
-Adhesive (main agent): polyester resin (manufactured by Rock Paint, trade name: RU-004) 89 parts by mass-Adhesive (curing agent): aliphatic polyisocyanate (manufactured by Rock Paint, trade name: H-1 ) 11 parts by mass / solvent: Methyl acetate (amount in which the proportion of all solids other than the solvent is 16% by mass)

When the obtained oxygen-absorbing barrier film was evaluated in the same manner as in Example 1, the total light transmittance was 90% and the haze was 1, indicating good transparency.
The oxygen absorption amount was 12 cc / 100 cm ² , indicating that there was sufficient oxygen absorption performance.
Further, in the sample after 30 days storage, the appearance change and mold generation on the surface of all the candy were not confirmed, and the packaging material storage suitability was sufficient.

[Example 10]
In Example 9, the oxygen-absorbing coating layer and linear low-density polyethylene of the laminate obtained by forming a coating film on the barrier surface of the transparent oxygen-absorbing barrier film using a sol solution as a coating liquid for coating A sample was prepared in the same manner as in Example 9 except that an adhesive layer was formed between the (LLDPE) film (thickness 50 μm, manufactured by Phutamura Chemical Co., Ltd., XMTN).
Thereby, transparent barrier PET (support base material (PET) and barrier layer), oxygen-absorbing coating layer, adhesive layer and sealant layer (LLDPE) were laminated in this order, and the support base material was disposed on the outermost surface. An oxygen-absorbing barrier film was produced.

When the obtained oxygen-absorbing barrier film was evaluated in the same manner as in Example 1, the total light transmittance was 92%, and the haze was 0, indicating good transparency.
Further, it was found that the oxygen absorption amount was 14 cc / 100 cm ² and there was sufficient oxygen absorption performance.
Furthermore, in the sample after 30 days of storage, no change in the appearance of the surface of all the ridges and generation of mold were confirmed, and the packaging material storage suitability was sufficient.

[Comparative Example 4]
A sample was prepared and evaluated in the same manner as in Example 9 except that the oxygen-absorbing material was not added to the sol solution as the coating coating solution.
As a result, the oxygen-absorbing barrier film had good transparency with a total light transmittance of 90% and a haze of 0.
Further, the oxygen absorption amount was 0 cc / 100 cm ^2, and it was confirmed that there was no oxygen absorption.
Furthermore, in the sample after 30 days storage, the occurrence of mold was confirmed on the surfaces of all the bags, and it was found that the packaging material storage suitability was not sufficient.

[Example 11]
A sample was prepared and evaluated in the same manner as in Example 1 except that silicon nitride particles (Nihon Ceratech, HM-5MF, average particle size 0.65 μm) were used instead of the spherical silica particles used as the carrier particles of the oxygen-absorbing material. Went.
As a result, the film showed good transparency with a total light transmittance of 85% and a haze of 3.
The oxygen absorption amount was 22 cc / 100 cm ² , confirming good oxygen absorption.
Furthermore, in the samples after 30 days storage, there is no change in appearance such as color or mold on the cut straw, no change in texture, no change in appearance such as discoloration or peeling of the pouch itself, and packaging material It was confirmed that it was suitable for storage.

[Example 12]
Example 1 except that silicon aluminum oxynitride (sialon, SiAlON) particles (manufactured by Neiji Jiko Co., Ltd., average particle size of 1 μm) were used instead of the spherical silica particles used as the carrier particles of the oxygen-absorbing material. Samples were prepared and evaluated.
As a result, the film showed good transparency with a total light transmittance of 88% and a haze of 2.
Further, it was confirmed that the oxygen absorption amount was 20 cc / 100 cm ² and showed good oxygen absorption.
Furthermore, in the samples after 30 days storage, there is no change in appearance such as color or mold on the cut straw, no change in texture, no change in appearance such as discoloration or peeling of the pouch itself, and packaging material It was confirmed that it was suitable for storage.

DESCRIPTION OF SYMBOLS 1 ... Barrier layer 2 ... Oxygen absorption layer 3 ... Adhesive layer 4 ... Sealant layer 5 ... Support base material 10 ... Packaging material

Claims (3)

Carrier particles;
Oxygen absorbing particles supported on the surface of the carrier particles and having a nano-order size;
Have
The carrier particles are particles of at least one oxide, nitride or oxynitride of metal and silicon;
The oxygen-absorbing particles, Ri Oh with particles of metal oxide having oxygen absorbing property,
An oxygen-absorbing material for packaging materials, characterized by having no oxygen-absorbing organic material. The oxygen-absorbing material for packaging materials according to claim 1 , wherein the carrier particles have a nano-order size. A barrier layer;
An oxygen absorbing layer disposed on one surface of the barrier layer and containing an oxygen absorbing material;
Have
The oxygen absorbing material is
Carrier particles;
Oxygen absorbing particles supported on the surface of the carrier particles and having a nano-order size;
Have
The carrier particles are particles of at least one oxide, nitride or oxynitride of metal and silicon;
The oxygen-absorbing particles, Ri Oh with particles of metal oxide having oxygen absorbing property,
A packaging material , wherein the oxygen-absorbing material does not have an oxygen-absorbing organic material.