JP6729524B2 - Oxygen absorbing material and packaging material - Google Patents

Description

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

In a package for packaging foods and 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 contents such as foods.
As such an oxygen absorbing material, an iron-based oxygen absorbing material containing iron as a main raw material is known. Further, the iron-based oxygen absorbing material is generally used by enclosing it in a small bag and then putting it in a package together with contents such as food.
As the oxygen absorber, an organic oxygen absorber using an oxygen-absorbing organic material is known. For example, as described in Patent Document 1, a method is known in which an organic oxygen absorber is contained in any one of layers of a laminate constituting a package.

International Publication No. 2015/146829

However, when the iron-based oxygen absorbing material is used in the form of a pouch containing the iron-based oxygen absorbing material, the iron-based oxygen absorbing material may drop together with the contents when the package is opened. Also, if the contents are food, there is a risk of accidental ingestion with the food.
Further, from the viewpoint of preventing accidental ingestion, it may be added to any layer constituting the package. However, iron-based oxygen absorbing materials usually have low transparency. Therefore, the package containing the iron-based oxygen absorbing material has a problem that the visibility of the contents is low.
On the other hand, the organic oxygen absorbing material has relatively high transparency. Therefore, the package to which the organic oxygen absorbing material is added has an advantage that the visibility of the contents can be maintained. However, since the organic oxygen absorbing material produces aldehydes and ketones as decomposition products along with the absorption of oxygen, there is a problem that an offensive odor is generated. Further, it is possible to separately form a layer for suppressing an offensive odor described in Patent Document 1 in addition to the oxygen absorption layer, but 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 a main object of the present invention is to provide an oxygen absorbing material having high transparency and reduced odor generation.

In order to achieve the above object, the present invention comprises carrier particles, and oxygen absorbing particles having a nano-order size, which are carried on the surface of the carrier particles, wherein the carrier particles are at least one of metal and silicon. Provided is an oxygen absorbing material, which is a particle of a seed oxide, a nitride, or an oxynitride, wherein the oxygen absorbing particle is a particle of a metal or a metal oxide having an oxygen absorbing property.

According to the present invention, the oxygen-absorbing particles having a nano-order size have a structure in which the oxygen-absorbing particles of the present invention are supported on the surface of the carrier particles composed of the above-mentioned material having high optical transparency, , Becomes highly transparent.
Further, since the oxygen-absorbing particles are particles of a metal or a metal oxide having an oxygen-absorbing property, the oxygen-absorbing material of the present invention has reduced odor generation.
From the above, the oxygen absorbing material of the present invention has high transparency and has 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 have excellent oxygen absorbing properties.

In the present invention, the oxygen-absorbing metal 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 have excellent oxygen absorbing properties.

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

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, wherein the oxygen absorbing material is a carrier particle and a surface of the carrier particle. And oxygen-absorbing particles having a nano-order size, wherein the carrier particles are particles of at least one oxide of metal and silicon, nitride or oxynitride, and the oxygen-absorbing particles are Provided is a packaging material characterized by being particles of a metal or a metal oxide having an oxygen absorbing property.

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

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

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 containing 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 has carrier particles and oxygen absorbing particles having a nano-order size, which are carried on the surface of the carrier particles, and the carrier particles are at least one of metal and silicon. The oxide, nitride, or oxynitride particles of 1. above, wherein the oxygen absorbing particles are particles of a metal or a metal oxide having an oxygen absorbing property.

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 made of metal or the like having low light transmittance.
Further, even if the average primary particle size is nano-order size, if the oxygen absorbing particles aggregate with each other to form an oxygen absorbing particle aggregate having an apparently large particle size, the transparency decreases.
However, by supporting the oxygen absorbing particles 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 it is possible to suppress a decrease in transparency due to aggregation or the like.
Furthermore, the constituent material of the carrier particles on which the oxygen-absorbing particles are carried is the above-mentioned highly transparent material, for example, even when the particle diameter of the carrier particles is larger than the particle diameter of the oxygen-absorbing particles, The carrier particles have high transparency.
From this, the oxygen-absorbing particles of nano-order size, which are composed of the above-mentioned material having low optical transparency, are supported on the surface of the carrier particles composed of the above-mentioned material of high optical transparency. By having the above, the oxygen absorbing material of the present invention has high transparency.

Further, since the oxygen absorbing particles are particles of a metal or a metal oxide having an oxygen absorbing property, the oxygen absorbing material of the present invention has, for example, generation of offensive odor due to generation of aldehyde or ketone. ..

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

The oxygen absorbing material of the present invention has carrier particles and oxygen absorbing particles.
Hereinafter, each component of the oxygen absorbing material of the present invention will be described.

1. Carrier Particles 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 their surfaces.

Here, carrying means to attach the oxygen absorbing particles to the surface of the carrier particles, and usually the carrier particles and the oxygen absorbing particles are attached so as to be in direct contact with each other by physical adsorption or the like.

The constituent material of the carrier particles is an oxide, nitride or oxynitride of metal, an oxide, nitride or oxynitride of silicon, or an oxide, nitride or oxynitride of metal and silicon.
Note that the above-mentioned 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 It may be referred to as an oxide or the like.) is contained as a main component of the above-mentioned constituent materials.
In addition, being contained as a main component means that the content of the above-mentioned oxide or the like is higher than 80 mass% of the constituent materials.
For example, when the constituent material is an oxide of silicon, the content of silicon oxide may be 80% by mass or more of the constituent material. When the constituent materials are oxides and nitrides of silicon, 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-mentioned oxide or the like is preferably 90% by mass or more of the constituent material, more preferably 95% by mass or more, and 100% by mass, that is, the constituent material is oxidized as described above. It is preferable that only the thing etc. 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, a nitride or an oxynitride of silicon (Si), or an oxide, a nitride or an oxynitride of a metal and silicon, among which silicon ( Si) is preferably an oxide, a nitride or an oxynitride, and particularly preferably an oxide of silicon (silicon oxide). This is because the above-mentioned constituent materials, particularly silicon oxide, have a high light-transmitting property, so that carrier particles having a high transparency can be formed.
In addition, since silicon oxide has water absorbability, by forming carrier particles using silicon oxide, the carrier particles absorb water in the air, etc., and develop oxygen absorbing ability with respect to oxygen absorbing particles. The required water can be easily supplied. Therefore, the oxygen-absorbing material of the present invention can easily exhibit the oxygen-absorbing ability of the oxygen-absorbing particles.

As the metal used for the metal oxide or the like of the carrier particles, oxides, nitrides, oxynitrides can be formed, as long as it can constitute the carrier particles having a desired light transmittance, for example, , Aluminum, zinc, cerium, titanium, indium, calcium, chromium, tin, zirconium, copper, niobium, antimony and the like are preferable, and among them, aluminum, zirconium and copper are preferable, and particularly aluminum and zirconium. Is preferred. This is because oxides and the like using the above metals have high light transmittance and can form carrier particles having high transparency. In addition, the above metals are preferable in terms of workability, durability and cost.

The oxides, nitrides or oxynitrides of metals and silicon are oxides, nitrides or oxynitrides containing both elements of metals and silicon, and specifically, silicon aluminum oxynitride (SiAlON), Examples thereof include silicon aluminum oxide (SiAlO).

The type of the constituent material is not limited to one type, and two or more types may be used. When there are two or more types of constituent materials, for example, carrier particles of oxide of which constituent material is silicon and carrier particles of oxynitride of constituent material of silicon can be mixed and used.
Further, in the case of two or more kinds, carrier particles formed of a mixture of both an oxide of silicon and an oxynitride may be used as the carrier particles.

The number of bonds of oxygen and nitrogen forming the oxide, nitride or oxynitride used in the above-mentioned constituent materials to the metal and silicon should be such that carrier particles having a desired light transmittance can be formed. For example, in the case of silicon oxide (SiOx), x is in the range of more than 0 and 2.0 or less, in the case of silicon nitride (SiNx), x is in the range of more than 0 and 1.33 or less, and in silicon oxynitride (SiOxNy), x and Each y can be in the range of more than 0 and 2.0 or less.
In the present invention, among others, it is preferable that the number of bonds of oxygen and nitrogen constituting the oxide, nitride and oxynitride to the metal and silicon is close to that satisfying the stoichiometric number, and the stoichiometric number is satisfied. It is preferable. The carrier particles have a small light absorption in the particle structure, and the refractive index thereof is close to that of the binder resin or the like used to disperse the oxygen absorbing material in the oxygen absorbing layer, so that the carrier particles have high transparency. Because it will be.
Here, as a material close to the one satisfying the stoichiometric number, for example, 90% or more of the stoichiometric number can be used.
For example, when the above-mentioned constituent material is silicon oxide (SiOx), x is preferably 1.8 or more, more preferably 1.9 or more, and particularly 2.0. It is preferable that they satisfy the stoichiometric number.

The average primary particle size of the carrier particles may be one that can support the oxygen absorbing particles, and is usually larger than the average primary particle size of the oxygen absorbing particles.
The average primary particle size of such carrier particles, for example, when used in a packaging material, may be any that can be well dispersed in a binder resin, and can be 100 μm or less, and a nano-order size. Is preferred. This is because when the carrier particles have a nano-order size, the oxygen absorbing material of the present invention has a small 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 particularly in the range of 0.1 nm to 500 nm. Is preferable, and particularly preferably within the range of 10 nm to 300 nm. This is because the oxygen absorbing material of the present invention has higher transparency when the average primary particle diameter is within the above range.
The average primary particle size can be determined by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, a particle image is measured with a transmission electron micrograph (TEM) (for example, H-7650 manufactured by Hitachi High-Tech), and an average value of the longest lengths of 100 or more randomly selected primary particles is measured. Can be the average primary particle size. It should be noted that 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 diameter of the carrier particles to the average primary particle diameter of oxygen absorbing particles (average primary particle diameter of carrier particles/average primary particle diameter of oxygen absorbing particles) may be greater than 1. , And preferably in the range of 10 to 1000, and more preferably in the range of 20 to 100. This is because when the above ratio is within the above range, the carrier particles can stably carry the oxygen absorbing particles.

The carrier particles may have any shape as long as they can support oxygen absorbing particles, and may have, 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, they have a larger surface area than when they have a solid structure. Therefore, the carrier particles can carry more oxygen absorbing particles.

From the viewpoint of stably supporting the oxygen-absorbing particles, the carrier particles may be subjected to any surface treatment such as hydrophilic treatment and water-repellent treatment.

The ratio of the oxygen-absorbing particles coated on the surface of the carrier particles (area covered by oxygen-absorbing particles on the surface of carrier particles/total surface area of carrier particles×100 (unit (%))) is Although it is appropriately set according to the mass ratio of 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, for example, 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%, and particularly, It is preferably in the range of 2% to 30%. This is because the oxygen absorption material has high transparency when the coating ratio is within the above range.
The method for measuring the coverage can be determined by observation with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
Further, S-4500 manufactured by Hitachi Ltd. can be used as the scanning electron microscope, and H-9000 manufactured by Hitachi Ltd. can be used as the transmission electron microscope.

The light transmittance of the carrier particles is not particularly limited as long as it can impart desired transparency to the oxygen absorbing material, and can be 75% or more, and particularly 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 in material selection.
Further, the light transmittance of the carrier particles means the total light transmittance of the measuring film dispersed in the transparent thermoplastic resin so that the content of the carrier particles becomes 30% by mass.
Furthermore, the total light transmittance can be measured according to JIS K7361-1 (Plastic-transparent material total light transmittance test method).

As a method for forming the film for measurement, use is made of a method in which 70 parts by mass of the transparent thermoplastic resin and 30 parts by mass of the carrier particles are uniformly mixed to prepare a resin composition, and a film having a thickness of 100 μm is formed. You can
Further, as a mixing method, for example, a method in which an extruder such as a TEM twin screw near continuous extruder manufactured by Toshiba Machine Co., Ltd. is used while stirring the transparent thermoplastic resin while heating and melting it can be used.
Further, as the 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, an extrusion film forming machine, a melt film forming machine, or the like may be used. it can.
As the transparent thermoplastic resin, except that carrier particles were not added, the total light transmittance and the haze of the transparent thermoplastic resin-only film formed by the same method as the method for forming the measuring film are, for example, 90. % And 0 can be used.
Specifically, as the transparent thermoplastic resin, a linear low-density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolution SP2020) can be used.

The haze of the carrier particles is preferably 3 or less, more preferably 2 or less. This is because if the degree of haze is large, the light diffusivity of the material is increased and the permeability of the material is reduced. The cloudiness (haze) can be obtained by measuring a measuring film used for measuring the light transmittance of carrier particles according to JIS K7136 (Plastic-Method for determining haze of transparent material).

2. Oxygen Absorbing Particle The oxygen absorbing particle is carried on the surface of the carrier particle and has a nano-order size.
The oxygen absorbing particles are particles of a metal or a metal oxide having an oxygen absorbing property.

Here, that the oxygen-absorbing particles have a nano-order size means that the average primary particle diameter of the oxygen-absorbing particles is a nano-order size.
In the present invention, the average primary particle diameter of the oxygen absorbing particles is preferably 500 nm or less, and particularly preferably in the range of 0.1 nm to 500 nm, particularly in the range of 0.1 nm to 100 nm. Is preferable, and in particular, the range of 0.1 nm to 50 nm is particularly preferable. This is because the average primary particle size makes the oxygen absorbing material highly transparent.
The method for measuring the average primary particle diameter can be the same as that described in the above section "1. Carrier particles".

The constituent material of the oxygen absorbing particles is a metal or a metal oxide having an oxygen absorbing property.
In the present invention, the constituent material is preferably a metal having oxygen absorbability.
This is because when the constituent material of the oxygen absorbing particles is a metal, the oxygen absorbing particles often have excellent oxygen absorbing properties. Further, since the metal has a low light-transmitting property, it is possible to more effectively exert the effect of obtaining an oxygen absorbing material having a high transparency when the metal is carried on the carrier particles.

As the above-mentioned metal, any metal having oxygen absorbability may be used.
Here, the substance having oxygen absorbability may be one capable of binding oxygen.
Examples of such a metal having oxygen absorption property include iron, manganese, platinum, aluminum, zinc, tin, magnesium, chromium, silicon, cerium, titanium, copper, and the like. Among them, iron, aluminum Is preferable, and iron is particularly preferable. This is because the above-mentioned metal can form oxygen-absorbing particles having excellent oxygen-absorbing properties.
The metal particles include particles whose surface is oxidized.
The metal particles may include a mixture containing two or more of the above metals, an alloy, or a mixture of oxides thereof.

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

The number of bonds of oxygen contained in the metal oxide to the metal may be one that does not satisfy the stoichiometric number, and for example, can be 80% or less of the stoichiometric number, and above all, 70%. It is preferably not more than 50%, more preferably not more than 50%. This is because the above-mentioned number of bonds makes the metal oxide excellent in oxygen absorption.
Specifically, when iron (III) oxide (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. It is preferably 2,1 or less, and particularly preferably 1.5 or less.

Examples of the method for forming such a metal oxide in an oxygen-deficient state include a method of extracting oxygen from the 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 type of the constituent material is not limited to one type, and two or more types may be used. When there are two or more types of constituent materials, for example, oxygen absorbing particles having a constituent material of iron and oxygen absorbing particles having a constituent material of iron oxide can be mixed and used.
Further, when there are two or more kinds, oxygen absorbing particles formed of a mixture of both oxygen and iron oxide may be used as the oxygen absorbing particles.

The shape of the oxygen absorbing particles may be the same as that of 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.

Content ratio of the oxygen absorbing particles to the carrier particles, that is, a mass ratio of the oxygen absorbing particles supported on one carrier particle (total mass of oxygen absorbing particles supported on the carrier particles/mass of carrier particles×100( (Unit (%))) may be in the range of 1% to 30%, preferably in the range of 1% to 20%, and particularly preferably in the range of 1% to 10%. Is preferred. This is because when the above mass ratio is within the above range, the oxygen absorbing material has excellent oxygen absorbing properties.

3. Oxygen Absorbing Material The light transmittance of the oxygen absorbing material of the present invention may be, for example, one capable of forming a highly transparent packaging material, and may be 70% or more, and particularly 80. % 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 it is usually 95% or less from the viewpoint of flexibility in material selection.
Further, the light transmittance of the oxygen absorbing material is similar to that of 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 measuring film, the same method as that described in the above section “1. Carrier particles” can be used, and the measuring film is formed by 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 required.
Examples of the other configuration include an oxygen absorption catalyst that is supported on at least one surface of the carrier particles and the oxygen absorbing particles and catalyzes the development of the oxygen absorbing performance of the oxygen absorbing particles.
Examples of the oxygen absorption catalyst include metal halides and the like 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., first, the particles in which the oxygen absorbing particles are supported on the surface of the carrier particles are prepared, and then an aqueous solution of metal halide or the like is sprayed Can be mentioned.

The method for producing the oxygen-absorbing material may be a method capable of supporting the oxygen-absorbing particles on the surface of the carrier particles, for example, a particle preparing step of preparing the carrier particles and the oxygen-absorbing particles, and both particles. There may be mentioned a method having a firing step of firing the dispersion fluid of both particles after preparing a uniformly dispersed dispersion fluid, and a pulverization step of pulverizing 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 size.
Examples of the forming method include a crushing method, a gas phase synthesis method, a liquid phase synthesis method, an aerosol heating method, and a sol-gel method. In addition, examples of the vapor phase growth method include a PVD (physical vapor phase growth) method and a CVD method (chemical vapor deposition method). Further, as the liquid phase growth method, 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 and high pressure (supercritical) hydrothermal synthesis method, etc. Any forming method can be used.
The average primary particle diameter of the carrier particles and the oxygen absorbing particles prepared in this step is, for example, the average primary particle diameter described in the above “1. Carrier particles” and “2. 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, but may also contain a resin material or the like if necessary.
As a method for preparing the mixture, for example, when dispersing both particles, put the particles in a solution containing an appropriate dispersant or resin material, shake, obtain a uniform dispersion using a bead mill or the like. Any method can be used.
As the dispersant and the resin material, a general dispersant or resin material used for fixing particles to each other by firing can be used.
The firing temperature and firing time of the mixture of both particles in the firing step, the surface of both particles are partially melted, by forming an intermediate layer in which the constituent materials of both particles are mixed at the interface of both particles, It is sufficient that 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 may be within a range of 0.5 hours to 48 hours.

As the pulverization method of the fired product in the pulverization step, a particle state by pulverizing the fired product, that is, a method in which carrier particles are not bonded to each other via oxygen absorbing particles can be used. Good.
Examples of the pulverization method include a method in which the fired product is dispersed in a suitable solvent and mechanical dispersion or surface chemical dispersion is performed.
As the mechanical dispersion method, an ultrasonic dispersion method, a method using a shearing field, a method in which calcined materials collide and disperse at high speed, beads, etc. are used, and calcined materials at contact points between media moving at high speed There may be mentioned a method in which impact or frictional force is applied to the particles to disperse them.
Examples of the above-mentioned interfacial scientific dispersion method include a method utilizing charging, pH adjustment, a dispersion method using a surfactant, a chemical surface modification method in which silane coupling treatment is performed on the surface, and a method using a polymer coating. You can

Further, as the above-mentioned manufacturing method, after preparing the carrier particles, the carrier particles are immersed in a solution containing an oxygen absorbing material (for example, an iron (II) chloride tetrahydrate in the case of an iron-based aqueous solution), A method of supporting the oxygen absorbing material on the carrier particles by using a chemical reaction can be mentioned.
Further, as the above-mentioned production method, a method of preparing carrier particles and then directly forming oxygen absorbing particles on the surface of the carrier particles by using a hydrothermal reaction or a supercritical reaction may be used.

4. Uses The oxygen-absorbing material of the present invention may be used as long as it requires absorption of oxygen, for example, an oxygen-absorbing layer arranged as an inner layer of the oxygen-barrier layer of a packaging material that requires oxygen-barrier properties, Oxygen absorption layer for removing residual oxygen in the packaging container, oxygen absorption material for inhibiting growth of aerobic microorganisms and insects, yellowing due to oxidation of sebum remaining on fibers, oxygen for suppressing vegetation of fungi and germs Examples include absorbing materials and members for oxidizing (corroding) metals.

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

Such a packaging material of the present invention will be described with reference to the drawings. FIG. 1 is a schematic 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 absorbing layer 2 that is disposed on one surface of the barrier layer 1 and contains an oxygen absorbing material. The absorbing material has carrier particles and oxygen absorbing particles having a nano-order size and carried on the surface of the carrier particles, wherein the carrier particles have at least one oxide of metal and silicon, a nitride, or The particles are oxynitride particles, and the oxygen absorbing particles are particles of a metal or a metal oxide having an oxygen absorbing property.
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 the adhesive layer 3.

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

The packaging material of the present invention has a barrier layer and an oxygen absorbing layer.
Hereinafter, each component of the packaging material of the present invention will be described in detail.

1. Placement 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 structure of such a packaging material, in addition to the barrier layer and the oxygen absorbing layer, an inner surface layer arranged on one surface of the barrier layer described in “4. Good.
Here, when the layer structure includes an inner surface layer, the oxygen absorbing layer may be arranged as an oxygen absorbing coating layer having only an oxygen absorbing function, but it is arranged integrally with the inner surface layer. The oxygen absorption layer may be arranged as the inner surface layer.
In the present invention, it is particularly preferable that the oxygen absorption layer is arranged as the inner surface layer.
By arranging the oxygen absorbing layer as the inner surface layer, the packaging material can have a small number of constituent layers and can be easily formed.
It should be noted that FIG. 1 described above shows an example in which the oxygen absorption layer 2 is arranged as an inner surface layer.

When the oxygen absorbing layer is arranged as an inner surface layer, it can be arranged as any layer included in the inner surface layer, but when the inner surface layer includes an adhesive layer for adhering two layers, an adhesive layer Are preferably arranged as.
For example, the layer structure of the packaging material has a layer structure having an adhesive layer and a sealant layer as an inner layer in this order on one surface side of the barrier layer, a support base material supporting the barrier layer, an adhesive layer and a sealant layer. In the case of a layered structure having the above in this order, the oxygen absorbing layer can be arranged as any layer of the inner surface layer, but among them, it is preferably arranged as an adhesive layer.
The adhesive layer can be easily formed after the shipping order, that is, immediately before the manufacturing 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 the shipping order, an adhesive stored in a state of not contacting oxygen is provided between the two prepared layers. It is possible to use a manufacturing method or the like in which an adhesive layer is formed by coating and adhering both layers. Therefore, by disposing the oxygen absorbing layer as the adhesive layer, it is possible to prevent the oxygen absorbing layer from absorbing oxygen before the packaging material packages the contents.
It should be noted that FIG. 1 described above shows an example in which the oxygen absorbing layer 2 is arranged as the adhesive layer 3 having the adhesive layer 3 and the sealant layer 4 as the inner surface layer.
Further, FIG. 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 arranged as the sealant layer 4, and FIG. 2B shows the support substrate as the inner surface layer. 5, the adhesive layer 3 and the sealant layer 4 are provided, and the oxygen absorbing layer 2 is arranged as the adhesive layer 3.

When the oxygen-absorbing layer is used as the oxygen-absorbing coating layer, the oxygen-absorbing layer may be arranged 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 may be a portion in contact with the surface on the side opposite to the layer, a portion sandwiched between the adhesive layer and the sealant layer, or the like.
Here, in FIG. 3, the packaging material 10 has a supporting base material 5, an adhesive layer 3 and a sealant layer 4 as inner surface layers, and an oxygen absorbing layer 2 as an oxygen absorbing coating layer. 2 shows an example in which 2 is arranged between the adhesive layer 3 and the sealant layer 4.

2. Oxygen Absorbing Layer The oxygen absorbing layer in the present invention is a layer which 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 of the barrier layer on the side where the contents 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 content described in the above section "A. Oxygen absorbing material", and therefore the description thereof is omitted here.

The content of the oxygen-absorbing material in the oxygen-absorbing layer may be any as long as it can impart desired oxygen-absorbing performance, and can be in the range of 3% by mass to 80% by mass, and 3% by mass to 50% by mass. The content is preferably in the range of mass%, and more preferably in the range of 3 mass% to 30 mass%. This is because when the content is within the above range, the oxygen absorption layer has excellent oxygen absorption.

The oxygen absorbing layer usually has a binder resin that disperses and holds an oxygen absorbing material and the like.
As such a binder resin, when the oxygen absorbing layer is disposed as the inner surface layer, the constituent material of each inner surface layer described in the section “4. Inner surface layer” described later can be used.
When the oxygen absorbing layer is included as the 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 sol-gel material cured. The thing etc. can be used. In the present invention, it is preferable that the binder resin is a thermoplastic resin. This is because the binder resin makes it easy to form the oxygen absorption layer.
Examples of the thermoplastic resin include polyethylene resins, polypropylene resins, polystyrene resins, vinyl resins such as polyvinyl chloride, polyester resins, and polyamide resins. Further, the thermoplastic resin may use only one type, or may use two or more types in combination. In the present invention, it is preferable that the thermoplastic resin is a polyethylene resin or a polypropylene resin.
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, an epoxy acrylate, a 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, the light or electron beam curable resin may use only one kind, or may use two or more kinds in combination.
As the cured product of the thermosetting resin, for example, a mixture of polymethylmethacrylate, polyacrylate, polycarbonate, methylphthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile and styrene copolymer. , Poly(-4-methylpentene-1), phenol resin, epoxy resin, cyanate resin, maleimide resin, polyimide resin and the like. Further, polyvinyl butyral, acrylonitrile-butadiene rubber, those modified with a polyfunctional acrylate compound, crosslinked polyethylene resin, a mixture of crosslinked polyethylene and epoxy resin, a mixture of crosslinked polyethylene and cyanate resin, polyphenylene ether and epoxy resin Examples thereof include a thermosetting resin modified with a thermoplastic resin such as a mixture, a mixture of polyphenylene ether and a cyanate resin. Further, the thermosetting resin may use only one kind, or may use two or more kinds in combination.
As a 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. You can 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 a (meth)acrylic polymer.

From the viewpoint of improving the light transmittance of the oxygen absorption layer, the binder resin preferably has a small refractive index with respect to the carrier particles in the oxygen absorption 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. When the refractive index difference is in the above range, the 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-Method of determining refractive index)), a spectroscopic ellipsometer, a reflectance measuring method, or the like. Further, the refractive index of the carrier particles can be measured by a method using an Abbe refractometer or 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, if necessary, from the viewpoint of more efficiently absorbing oxygen by the oxygen absorbing material.
Examples of the oxygen absorbing catalyst include sodium chloride (NaCl), sodium fluoride (NaF), and sodium bromide (when the constituent material of the oxygen absorbing particles is iron, aluminum, titanium, cerium, zinc, etc. Examples thereof include metal halides such as NaBr), potassium chloride (KCl), potassium fluoride (KF), and potassium bromide (KBr).
The content of the oxygen absorption catalyst can be appropriately set depending on the application of the oxygen absorption layer, and the like, for example, in the range of 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the oxygen absorbing material. Can be within.

The oxygen absorbing layer may have an additive as necessary within a range that does not impair the oxygen absorbing property, the transparency and the like of the oxygen absorbing layer.
Examples of the additives include known additives used for packaging materials such as plasticizers, antistatic agents, and coloring materials.
Further, the content of the above-mentioned additive can be appropriately set according to the kind of the additive and the like.

(2) Others The thickness of the oxygen absorbing layer may be in the range of 1 μm to 120 μm, and particularly 3 μm to 80 μm as long as it can form an oxygen absorbing layer having a desired oxygen absorbing property. It is preferably within the range. When the thickness is within the above range, the oxygen absorption layer has excellent oxygen absorption.

The light transmittance of the oxygen absorbing layer may be any 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. This is because the packaging material of the present invention has high transparency when the light transmittance is within the above range.
The light transmittance of the oxygen absorbing layer is the total light transmittance of the oxygen absorbing layer.

The haze of the oxygen absorbing layer can be, for example, 3 or less, preferably 2 or less, and particularly preferably 1 or less. When the haze is within the above range, the packaging material of the present invention has high transparency.
The haze of the oxygen absorbing layer can be measured in accordance with JIS K7361-1 (Plastic-Method for obtaining haze of transparent material).

The method for forming the oxygen absorbing layer may be any method capable of forming an oxygen absorbing layer having a desired thickness.
As the forming method, for example, when the binder resin is a thermoplastic resin, a method of heating and melting the constituent materials to form a film in a desired shape can be mentioned.
Examples of the film forming method include an extrusion molding method using a T-die, an inflation method, and the like.
Further, as the forming method, as the oxygen absorbing layer forming composition, a composition containing a solvent capable of dispersing or dissolving the constituent materials is used, and the oxygen absorbing layer forming composition is applied to form the oxygen absorbing layer. A method can be mentioned. In addition, the above-mentioned forming method may be a treatment of drying and removing the solvent from the coating film of the composition for forming the oxygen-absorbing layer, a curing treatment or the like, if necessary.
Examples of the above-mentioned coating method include known coating methods such as roll coating, gravure coating and kiss coating. The curing treatment differs depending on the binder resin, and when the binder resin is a thermosetting resin, a heating method can be mentioned.

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

Here, the oxygen permeability (23° C. 65% RH) of the barrier layer may be any as long as a packaging material having a desired oxygen barrier property can be obtained, and for example, 0.5 cc·m ⁻² ·day ^−. It can be ¹ ·atm ⁻¹ or less.
The oxygen permeability can be obtained according to JIS K7126.

The type of 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, the above type is preferably a resin layer or a metal oxide vapor-deposited layer from the viewpoint of making the packaging material highly transparent.
The resin material forming the resin layer may be any material that can impart desired oxygen barrier properties, and examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymer described in International Publication No. 2015/046485. Can be mentioned.
The metal oxide forming the vapor-deposited layer may be any one that can impart desired oxygen barrier properties, and examples thereof include silicon oxide and aluminum oxide described in WO 2015/046485. ..
The metal forming the vapor deposition layer may be any metal that can impart a desired oxygen barrier property, and examples thereof include silicon and aluminum described in JP-A-2005-208867.
Examples of the metal forming the metal foil layer include aluminum described in International Publication No. 2015/046485.
Further, 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. As the gas barrier coating film, for example, those described in JP 2012-35516 A, International Publication No. 2015/046485, etc. can be used.

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, and for example, when the type is a resin layer, it can be set within the range of 10 μm to 30 μm.
Further, when the above-mentioned type is a vapor deposition layer, it can be set in the range of 50Å to 4000Å.
Further, when the type is a metal foil layer, the thickness can be within the range of 5 μm to 20 μm.

As the method for forming the oxygen barrier layer, a known forming method depending on the type of the oxygen barrier layer can be used.

4. Inner surface layer The packaging material of the present invention has at least a barrier layer and an oxygen absorbing layer, but may have an inner surface layer disposed on one surface of the barrier layer, if necessary.
Such an inner surface layer may be disposed on one surface of the barrier layer and included in the package when the package is formed. For example, a sealant layer and a barrier layer used for forming the package are supported. Examples of the supporting substrate include an adhesive layer for adhering two layers, and the like.
In the present invention, the inner surface layer usually contains a sealant layer. By including the sealant layer as the inner surface layer, the packaging material of the present invention facilitates the production of a package.
Further, in the present invention, it is preferable that the inner surface layer has an adhesive layer. By having the adhesive layer, it becomes possible to prepare layers other than the adhesive layer in advance and flexibly adjust the layer configuration and the like according to the contents of the shipping order.
For example, a barrier layer and a sealant layer are prepared in advance, and after a shipping order, an adhesive is applied between the two prepared layers to form an adhesive layer for adhering the two layers, thereby forming a desired layer. This is because the packaging material having the contents of the shipping order can be easily manufactured.

(1) Sealant layer The sealant layer is used for forming a package.
Here, as what is used for forming the package, for example, two packaging materials are arranged and overlapped so that the sealant layers face each other, and the peripheral end portions are heated so that the sealant layers are arranged to face each other. And the like, which are used for forming the seal portion by melting and fusing each other.
Moreover, since it is used for forming 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, and for example, a polyolefin-based material having a heat-sealing property described in WO 2015/046485 and the like. Resin etc. can be used.

When the sealant layer is not used as the oxygen absorbing layer, the thickness of the sealant layer may be, for example, one having adhesiveness capable of forming a packaging container having desired strength, and may be in the range of 10 μm to 200 μm. be able to.

As a method for forming the sealant layer, a known forming method such as the method described in WO 2015/046485 can be used.
Specifically, the forming method can be the same as the content described in the above section “2. Oxygen absorbing layer”.

(2) Adhesive layer The above-mentioned adhesive layer adheres two layers.
The two layers adhered by such an adhesive layer may be any layers other than the adhesive layer, for example, an oxygen absorbing layer as an oxygen absorbing coating layer, a barrier layer, and a supporting substrate. Or, it may be between the sealant layer, the barrier layer and the support base material or the sealant layer, the support base material and the sealant layer, and the like.
In addition, the adhesive layer is usually used for bonding two layers prepared in advance.

The constituent material of the adhesive layer may be an adhesive capable of bonding members arranged on both sides of the adhesive layer with desired strength, for example, a thermosetting adhesive, an ultraviolet curable adhesive, A cured product such as an electron beam curable adhesive can be used.
Further, as the above-mentioned adhesive, a solidified product of a hot-melt type adhesive, a pressure-sensitive adhesive or the like can be used.

Specific examples of the thermosetting adhesive, the ultraviolet curable adhesive, and the electron beam curable adhesive include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymer, and polyacrylic acid. Polyacrylic acid-based adhesives, cyanoacrylate-based adhesives, and copolymers of polystyrene with polystyrene, polyester, polyvinyl acetate, etc. Copolymerization with ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, and other monomers Ethylene copolymer adhesives, cellulosic adhesives, polyurethane adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, polyolefin adhesives, urea resins or melamine resins, etc. -Based adhesives, phenolic resin-based adhesives, epoxy-based adhesives, reactive (meth)acrylic-based adhesives, chloroprene rubber, nitrile rubber, elastomer adhesives such as styrene-butadiene rubber, silicone-based adhesives, alkali metals Inorganic adhesives made of silicate, low melting point glass, etc. may be mentioned. In addition, these adhesives may be used as a mixture of two or more kinds, if necessary.

Examples of the hot-melt adhesive include thermoplastic resins such as polyvinyl acetate resins described in JP-A No. 11-170791.
The above thermoplastic resins may be used as a mixture of two or more, if necessary.

Examples of the pressure-sensitive adhesive include acrylic adhesives, natural rubber adhesives, synthetic rubber adhesives, and the like.
The pressure-sensitive adhesive may be used as a mixture of two or more kinds as necessary.

The thickness of the adhesive layer may be such that the members arranged on both sides of the adhesive layer can be bonded to each other with desired strength, and for example, the coating amount in a dry state is 0.1 g/m 2. ^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 forming method can be the same as the content described in the above section “2. Oxygen absorbing layer”.

(3) Supporting Base Material The supporting base material supports the barrier layer, and is particularly used when a vapor deposition layer is used as the barrier layer.
Further, since it is used for supporting the barrier layer, the supporting substrate is usually arranged so as to be in contact with the barrier layer.

As a constituent material of such a supporting substrate, any material that can stably support the barrier layer may be used, and for example, a resin material such as a polyester-based resin or a polypropylene-based resin described in WO 2015/046485 or the like. Can be used.
When the above-mentioned supporting base material is not used as the oxygen absorbing layer, the thickness of the supporting base material may be such that it can stably support the barrier layer, and for example, it can be in the range of 6 μm to 100 μm.

The method for forming the supporting base material may be any method as long as a supporting base material having a desired thickness can be obtained, and for example, the same as the contents described in the above section “2. oxygen absorbing layer”. 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 which is disposed on the surface of the sealant layer opposite to the barrier layer and is removed by peeling when the package is formed.
Examples of the gas barrier release layer include those described in International Publication No. 2015/046485.

6. Packaging Material The light transmittance of the packaging material of the present invention may be any as long as it exhibits desired transparency, and can be, for example, 70% or more, preferably 80% or more, and particularly preferably It is preferably 85% or more. This is because the packaging material of the present invention has high transparency when the light transmittance is within the above range.
The above-mentioned light transmittance refers to the total light transmittance of the packaging material.

The haze of the packaging material can be, for example, 3 or less, preferably 2 or less, and particularly preferably 1 or less. When the haze is within the above range, the packaging material of the present invention has high transparency.

The manufacturing method of the packaging material of the present invention may be any method capable of accurately laminating each of the above-described components, for example, a preparatory step of preparing a layer other than the oxygen-absorbing layer in advance, and a layer other than the oxygen-absorbing layer. An oxygen absorbing layer forming step of applying an oxygen absorbing layer forming composition to the surface to form an oxygen absorbing layer can be mentioned.
More specifically, when the layer structure of the packaging material is a layer structure in which a barrier layer, a supporting base material, an oxygen absorbing layer as an adhesive layer and a sealant layer are laminated in this order, the supporting base material and the supporting base material A barrier laminate including a barrier layer formed on a base material and a sealant layer are prepared, and after the shipping order, the oxygen absorbing layer forming composition is applied between the barrier laminate and the sealant layer. Therefore, a method of disposing an oxygen absorbing layer as an adhesive layer can be mentioned.
Further, when the layer structure is a layer structure in which a barrier layer, a supporting base material and an oxygen absorbing layer as a sealant layer are laminated in this order, a barrier laminate is prepared, and after the shipping order, the barrier laminate is prepared. A method of arranging the oxygen absorbing layer as a sealant layer by applying the composition for forming an oxygen absorbing layer on the surface of the supporting substrate contained in the body can be mentioned.

When the layer structure is a layer structure in which a barrier layer, a supporting base material, an adhesive layer, an oxygen-absorbing coating layer and a sealant layer are laminated in this order, the manufacturing method includes a barrier laminate. And a sealant layer having an oxygen-absorbing coating layer formed on its surface, and after the shipping 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 the two layers with an adhesive layer may be used.

As a method for forming a package using the packaging material of the present invention, known methods described in, for example, JP2002-192646A and JP2012-35516A can be used.
Specifically, in the case where the packaging material has a sealant layer, the above-mentioned forming method is such that two packaging materials are arranged and overlapped so that the sealant layers of the respective packaging materials face each other, and the peripheral end portion It is possible to use a method in which the sealant layers are formed by heating and melting the sealant layers arranged to face each other and fusing each other.
When the sealant layer is not provided as the packaging material, the above-mentioned forming method may be a method of adhering the peripheral end portions of the two packaging materials using an adhesive agent prepared separately.

7. Uses The use of the packaging material of the present invention may be any as long as it is used for forming a packaging body which requires transparency and oxygen absorbability in the inner layer of the oxygen barrier layer.
Examples of uses of such a package include foods, pharmaceuticals, industrial materials, batteries such as lithium-ion batteries, electronic devices, electronic parts, and the like, which are used for packaging contents that cause quality deterioration due to the presence of oxygen. be able to.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, has substantially the same configuration as the technical idea described in the scope of the claims of the present invention, and any one having the same operational 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 (HPS-3500 (average particle size 3.5 μm) manufactured by Toagosei Co., Ltd.) were prepared as carrier particles.
Next, as oxygen absorbing particles, iron particles having oxygen absorbing property were produced by a direct reduction method.
Specifically, first, iron (II) chloride tetrahydrate (FeCl ₂ .4H ₂ O; manufactured by Wako Pure Chemical Industries, Ltd.) 0.92 mmol, sodium hydroxide (NaOH; manufactured by Wako Pure Chemical Industries Ltd.) 0. 92 mmol was dissolved in 450 mL of ion-exchanged water. The solution was transferred to a three-necked flask, stirred while flowing N ₂ gas, and cooled in an ice bath to bring 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.) were dissolved in 50 ml of ion-exchanged water, and the solution was put into a stirring three-necked flask to precipitate iron particles. Obtained.
The precipitate was washed with ion-exchanged water and ethanol to obtain iron particles. When the particle size of these 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 heat-treated at 600° C. for 3 hours in a nitrogen atmosphere, and then acetic acid. It was dissolved in a mixed solution of ethyl (Wako Pure Chemical Industries, Ltd.) and PGME (propylene glycol monomethyl ether; Showa Denko KK) 8:2.
Thereafter, the zirconia beads were shaken with 2 mmφ for 1 hour, and further with 0.1 mmφ zirconia beads for 2 hours to prepare a uniformly dispersed oxygen absorbing material (silica-supported iron particle) solution.

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

(Admixture ratio of adhesive composition)
-Oxygen absorbing material: 43 parts by mass of the above-mentioned oxygen absorbing material (silica-supported iron particles)-Adhesive (main agent): Polyester resin (Rock Paint Co., trade name: RU-004) 54 parts by mass-Adhesive (curing agent) ): Aliphatic polyisocyanate (manufactured by Rock Paint, trade name: H-1) 3 parts by mass Dispersant: Alkylammonium salt polymer 21.5 parts by mass (50 parts by mass for 100 parts by mass of oxygen absorbing material)
Oxygen absorption initiation 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 (the amount 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 size) in which a silicon-based barrier layer was formed on the surface of a PET film as a supporting substrate was prepared by using the above adhesive composition. It was coated on the surface of the PET substrate (trade name: IB-PET-PIR, manufactured by Nippon Printing Co., Ltd.) using a Meyer bar so that the dry coating amount was 9 g±1 g/m ² . A coating film of the adhesive composition was prepared by drying at 70°C for 30 seconds.
A film coated with this adhesive composition is laminated by linear compression bonding with a linear low-density polyethylene (LLDPE) film (thickness 50 μm, XMTN manufactured by Futamura Chemical Co., Ltd.) at 80° C. using a roller, and then, A transparent barrier PET film (barrier layer and supporting base material (PET)), an adhesive layer (cured material layer of the adhesive composition), and LLDPE are sequentially processed in this order by performing heat aging treatment in the atmosphere at 40° C. for 3 days. An oxygen-absorbing barrier film having a thickness of 70 μm was obtained.

(4) Evaluation of oxygen-absorbing barrier film With respect to the obtained oxygen-absorbing barrier film, total light transmittance, haze, oxygen-absorbing property, and packaging material form aptitude were evaluated.

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

(B) Oxygen-absorbing property The oxygen-absorbing barrier film was cut into 100 cm ² and sealed in a glass bottle with a lid (volume: 106 cc) together with 15 cc of distilled water. At this time, a sensor chip (SP-PSt3-NAU-D5, PreSens, Inc.) for measuring the oxygen concentration was fixed on the wall surface of the glass bottle in the glass bottle with an adhesive from the outside of the glass bottle in a direction that could be measured by the sensor.
Then, the oxygen concentration in the glass bottle after 720 hours has elapsed is measured using an oxygen concentration meter (Fixbox3, PreSens Co.), and the residual oxygen amount is calculated by converting the actual volume of the glass bottle into oxygen from the initial oxygen concentration. The amount of absorption was calculated. It was found that the oxygen absorption amount 720 hours after the sealing was 15 cc/100 cm ^2, which was a sufficient oxygen absorption amount.
It was determined that the oxygen absorption performance of 10 cc/100 cm ² or more was sufficient.

(C) Packaging material morphology evaluation Two pieces of oxygen-absorbing barrier film were used to fill the contents with cut rice cake (Sato Foods Co., Ltd., sugar cut rice cake 50 g/piece), and three-way heat seal into a size of 60 mm x 110 mm x 23 mm. Then, the remaining one side was heat-sealed to prepare a pouch, and a storage test was performed at room temperature (N=5 pieces). As a result, even after storage for 30 days, there was no change in appearance such as color and mold on the rice cake, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. It was confirmed that there is no packaging material storage suitability.

[Example 2]
An oxygen-absorbing barrier film was produced in the same manner as in Example 1 except that Sigma-Aldrich Nanopowder (product number: 746835, average particle size 25 nm) was used in place of the oxygen-absorbing particles (iron particles) prepared in Example 1. An evaluation was carried out.
As a result, the total light transmittance was 91% and the haze was 0, indicating good transparency.
Further, it was confirmed that the oxygen absorption amount was 30 cc/100 cm ² and that the oxygen absorption property was excellent.
Furthermore, the sample after storage for 30 days had no change in appearance such as color and mold on the rice cake, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. 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, it was confirmed that the oxygen absorption amount was 0 cc/100 cm ^2, and there was no oxygen absorption.
Furthermore, in the sample stored for 30 days, generation of mold was confirmed on the surface of all rice cakes, and it was found that the suitability for storage of the packaging material was not sufficient.

(Admixture 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 of all solids other than solvent is 16% by mass)

[Comparative example 2]
An oxygen-absorbing barrier film was produced 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 pulverizing method were used as the oxygen-absorbing particles.
As a result, the total light transmittance was 50% and the haze was 15, indicating no transparency.
Further, it was found that the oxygen absorption amount was 10 cc/100 cm ^2, which was a sufficient oxygen absorption amount.
Furthermore, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Example 3]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that nanoparticles (product number: 746878, average particle size 70 nm) manufactured by Sigma-Aldrich were used as the oxygen-absorbing particles (iron particles).
As a result, the total light transmittance was 90% and the haze was 1, indicating good transparency.
In addition, it was confirmed that the oxygen absorption property was 20 cc/100 cm ² , which was excellent.
Furthermore, the sample after storage for 30 days had no change in appearance such as color and mold on the rice cake, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. 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 HPA-0500 (average particle size: 0.75 μm) manufactured by Toagosei Co., Ltd. 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.
Further, it was found that the oxygen absorption amount was 20 cc/100 cm ^2, which was a sufficient oxygen absorption amount.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Example 5]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that Hipresica FR (product number N2N, average particle size 0.2 μm) of Ube Eximo Co. was used as the carrier particles (spherical silica particles).
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 23 cc/100 cm ^2, which was a sufficient oxygen absorption amount.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Example 6]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 1 except that spherical alumina (product number DAM03, average particle diameter 6.0 μm) manufactured by Denka Corporation was used as the carrier particles.
As a result, the total light transmittance was 87% and the haze was 2, showing good transparency.
It was also found that the oxygen absorption amount was 14 cc/100 cm 2, which was a sufficient oxygen absorption amount.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Example 7]
An oxygen-absorbing barrier film was prepared and evaluated in the same manner as in Example 2 except that a titanium oxide material manufactured by Ishihara Sangyo Co., Ltd. (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.
It was also found that the oxygen absorption amount was 22 cc/100 cm 2, which was a sufficient oxygen absorption amount.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

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

(Admixture 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 of all solids other than 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, showing good transparency.
Further, it was found that the oxygen absorption amount was 13 cc/100 cm ² and that there was sufficient oxygen absorption performance.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Comparative Example 3]
A sealant film with a thickness of 100 μm was produced with a lab inflation film-forming machine using only a linear low-density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolution 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 had a total light transmittance of 90% and a haze of 0, indicating good transparency.
Further, it was confirmed that the oxygen absorption amount was 0 cc/100 cm ² and that there was no oxygen absorption. Furthermore, in the sample stored for 30 days, generation of mold was confirmed on the surface of all rice cakes, and it was found that the suitability for storage of the packaging material was not sufficient.

[Example 9]
An oxygen absorbing material (silica-supported iron particles) solution was prepared in the same manner as in Example 1.
Next, a solution prepared so that 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 oxygen-absorbing material were added to 100 g of the solution stirred for 5 hours, and 2.5 100 ml of a polyvinyl alcohol aqueous solution adjusted to wt% was added and stirred for 3 hours to prepare a sol solution as a coating liquid for coating for forming an oxygen-absorbing coating layer.

Further, after spin coating the above sol solution on the PET substrate side surface of a transparent barrier PET (polyethylene terephthalate) film (thickness 12 μm, manufactured by Dai Nippon Printing Co., Ltd., trade name IB-PET-PIR), at 70° C. It was dried for 1 hour to prepare a laminate in which an oxygen-absorbing coating layer having a coating film of 2 μm was laminated.

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

(Admixture 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 of all solids other than 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, showing good transparency.
Further, it was found that the oxygen absorption amount was 12 cc/100 cm ² and that there was sufficient oxygen absorption performance.
Further, in the sample after storage for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material was sufficient.

[Example 10]
In Example 9, an oxygen-absorbing coating layer and a linear low-density polyethylene of a laminate obtained by forming a coating film on the barrier surface of a 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, XMTN manufactured by Futamura Chemical Co., Ltd.).
As a result, the transparent barrier PET (supporting substrate (PET) and barrier layer), the oxygen absorbing coating layer, the adhesive layer and the sealant layer (LLDPE) were laminated in this order, and the supporting substrate was placed 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 that there was sufficient oxygen absorption performance.
Furthermore, in the sample stored for 30 days, no change in the appearance of the surface of all rice cakes and generation of mold were confirmed, and the suitability for storage of the packaging material 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 liquid for coating.
As a result, the oxygen absorbing barrier film had a total light transmittance of 90% and a haze of 0, indicating good transparency.
Further, it was confirmed that the oxygen absorption amount was 0 cc/100 cm ^2, and there was no oxygen absorption.
Furthermore, in the sample stored for 30 days, generation of mold was confirmed on the surface of all rice cakes, and it was found that the suitability for storage of the packaging material was not sufficient.

[Example 11]
Sample preparation and evaluation were performed in the same manner as in Example 1 except that silicon nitride particles (Japan Ceratech Co., Ltd., 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. I went.
As a result, the total light transmittance of the film was 85%, and the haze was 3, showing good transparency.
Further, it was confirmed that the oxygen absorption amount was 22 cc/100 cm ² and that the oxygen absorption property was excellent.
Furthermore, the sample after storage for 30 days had no change in appearance such as color and mold on the rice cake, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. It was confirmed that it was suitable for storage.

[Example 12]
The same as in Example 1 except that silicon aluminum oxynitride (sialon, SiAlON) particles (manufactured by Ninji Iron Works Co., Ltd., average particle size 1 μm) were used instead of the spherical silica particles used as the carrier particles of the oxygen absorbing material. A sample was prepared and evaluated.
As a result, the total light transmittance of the film was 88% and the haze was 2, showing good transparency.
Further, it was confirmed that the oxygen absorption amount was 20 cc/100 cm ² and that the oxygen absorption property was excellent.
Furthermore, the sample after storage for 30 days had no change in appearance such as color and mold on the rice cake, no change in texture, and no change in appearance such as discoloration or peeling of the pouch itself. 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... Supporting base material 10... Packaging material

Claims (4)

Carrier particles,
On the surface of the carrier particles, oxygen-absorbing particles of 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 are metal particles having oxygen-absorbing property ,
An oxygen-absorbing material for a packaging material, which does not have an oxygen-absorbing organic material. The package according to claim 1 , wherein the oxygen-absorbing metal contains at least one of iron, manganese, platinum, aluminum, zinc, tin, magnesium, chromium, silicon, cerium, titanium and copper. Oxygen absorbing material for materials. The oxygen absorbing material for a packaging material according to claim 1, wherein the carrier particles have a nano-order size. A barrier layer,
An oxygen absorbing layer, which is disposed on one surface of the barrier layer and contains an oxygen absorbing material,
Have
The oxygen absorbing material,
Carrier particles,
On the surface of the carrier particles, oxygen-absorbing particles of 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 are metal particles having oxygen-absorbing property ,
A packaging material , wherein the oxygen-absorbing material does not have an oxygen-absorbing organic material.

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