JP3134291B2 - Oxygen absorbing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention has a function of absorbing moisture, oxygen, acidic substances, etc., and is used for metals, metal products, dried foods, pharmaceuticals, photographic films, ancient documents, and paintings. The present invention relates to a composition for absorbing oxygen, which is suitably used for storing pressed flowers and the like.

(Prior Art) Japanese Patent Publication No. Sho 62-040880 has proposed a method using an oxygen absorbent containing catechol, ascorbic acid and metal powder as main components as an oxygen absorbent. However, these oxygen absorbers need moisture to absorb oxygen, and when they coexist with the oxygen absorber, they have the drawback of rusting on the metal surface due to the evaporation of moisture and the dampness of the storage object. . As a method for preventing the evaporation of water, a method using a combination of an oxygen absorbent and a desiccant has been proposed in JP-A-56-15378.
However, in this method, moisture was transferred from the oxygen absorbent to the desiccant, and oxygen absorption was stopped halfway, or the drying function of the desiccant was reduced. Due to the stoppage of the oxygen absorption and the oxygen permeating from the packaging film packaging the object, there is a problem that the oxygen concentration in the system increases and the preservation effect disappears.

As a method for improving the disadvantages of such oxygen absorbers, Japanese Patent Application Laid-Open No.
JP-A-1555641, JP-A-63-198962, JP-A-1-67252, and JP-A-61-285973 have proposed an oxygen absorbent containing an unsaturated fatty acid compound as a main component. However, the oxygen absorption rate and the amount of oxygen absorption are small, so that the amount of the oxygen absorbing composition used increases, or when used for long-term storage, the oxygen concentration in the container sealed with the object to be preserved is slightly reduced in the container. Due to the fact that it gradually increases due to the infiltration of oxygen and moisture, the preservation effect of the object has a limit.

(Problems to be Solved by the Invention) The present invention relates to a method for preserving an article using an oxygen-absorbing composition, wherein the oxygen-absorbing composition of the oxygen-absorbing composition has an increased oxygen absorption rate and an increased oxygen absorption to improve the preservation effect of the object to be preserved. With the goal.

(Means of the Invention) The present invention has an unsaturated aliphatic hydrocarbon or a mixture of an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound as a main component,
The present invention relates to an oxygen absorbing composition in which a mixture of a main agent and a catalyst is supported on a support.

The oxygen absorbing composition of the present invention exhibits a preserving effect by absorbing oxygen. This composition comprises a main agent for absorbing oxygen and a substance for promoting oxygen absorption. The main agent is an unsaturated aliphatic hydrocarbon or a mixture of an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound. Examples of the substance that promotes oxygen absorption include a catalyst, an adsorbent, a basic substance, and a carrier. Note that the adsorbent may also serve as a carrier.

That is, the composition of the present invention comprises an unsaturated aliphatic hydrocarbon,
Alternatively, a mixture of an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound (A) may be added with a basic substance (B), an adsorbent (C), a catalyst (D), a carrier (E), and a heat generation preventer (F). From within
It is a composition to which two or more kinds including a catalyst (D) and a support (E) are added. The unsaturated aliphatic hydrocarbon of the present invention is a main agent that absorbs oxygen and is an unsaturated aliphatic hydrocarbon having an unsaturated bond and having 7 or more carbon atoms. Specific examples of the unsaturated aliphatic hydrocarbon include a polymer of isoprene or butadiene, a polymer of acetylene, and squalene.

Unsaturated fatty acid compounds, specifically, oleic acid, linolenic acid, linoleic acid, unsaturated fatty acids such as succinic acid and animal oils which are triglycerides of these unsaturated fatty acids,
Vegetable oils and their transition metal salts. This unsaturated fatty acid transition metal salt can also be used as a catalyst.

These unsaturated aliphatic hydrocarbons are used as one kind or a mixture of two or more kinds, and the mixture of the unsaturated aliphatic hydrocarbon and the unsaturated fatty acid compound is used as one kind or a mixture of two or more kinds.

The basic substance (B) is an acidic substance generated by the absorption of oxygen by an unsaturated aliphatic hydrocarbon or unsaturated fatty acid compound, or a substance that adsorbs an acidic substance in the system or absorbs moisture. . Specific examples include oxides, hydroxides, carbonates, organic acid salts and amine compounds of alkali metals and alkaline earth metals. Preferable are oxides of alkaline earth metals, and particularly preferable are casium oxide and magnesium oxide which absorb moisture simultaneously with an acidic substance.

The adsorbent (C) is a decomposed substance generated by the absorption of oxygen by an unsaturated aliphatic hydrocarbon or unsaturated fatty acid compound, or a substance that adsorbs moisture and increases the oxygen absorption rate or facilitates the production of a composition. It is. Specific examples include silica gel, activated clay, zeolite, activated carbon, perlite, and the like.

Further, a liquid organic substance such as glycerin having an equilibrium humidity of 70 RH% or less used as a humidity control agent is also included (hereinafter, a substance that adsorbs moisture is referred to as a desiccant).

The catalyst (D) increases the oxygen absorption rate of the main agent, and is a transition metal and / or a compound thereof. Specifically, transition metals such as iron, cobalt, chromium, copper, nickel and the like and inorganic compounds such as sulfates, chlorides and nitrates, organic acid salts such as fatty acid salts, and complex compounds with amine compounds And the like.

The support (E) supports the main agent and maintains the shape of the composition, while increasing the contact area with oxygen to increase the oxygen absorption rate. Specifically, paper made of pulp,
It is a nonwoven fabric made of an olefin resin such as polyethylene, or a granular material such as silica gel, activated clay, zeolite, activated carbon, and pearlite. The carrier is impregnated with or mixed with the main agent of the oxygen absorbing composition of the present invention. Use it.

The heat release inhibitor (F) is a substance added to prevent a large amount of packages from generating heat when exposed to the atmosphere and spontaneously igniting.
It is a substance that becomes liquid at any temperature from 230 ° C to 230 ° C and shows fluidity.

This oxygen absorbing composition is not particularly limited as long as it is a composition in which an unsaturated aliphatic hydrocarbon or a mixture of an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound is used as a main component, and a mixture of the main component and a catalyst is supported on a carrier. The composition-1 comprises (A), (B), (E) (or (C)) and (D), (A), (B) and (E) (or (C)). (A), (B), (C), (D) and (E), and (A) and (E) (or A composition-4 comprising (C)) and (D);
In particular, Composition-1, which is a granular bulk powder, is preferable from the viewpoint of oxygen absorption performance. Composition 3 in sheet form
Is preferable because no dust is generated.

Alternatively, the composition-1 or the composition-2 can be pressed into a tablet.

The production of these compositions is not particularly limited, but after adding (D) to (A), this is supported on (C),
(B) and / or (F) is coated on the surface to produce, or (A), (B), (C), (D),
(F) a granulation method in which a plurality of mixtures composed of the respective combinations are further uniformly mixed and granulated, or a sheet in which (D) is added to (A) and then impregnated in (E) ( A method for producing a sheet by laminating I) and a sheet (II) in which a liquid organic substance and / or an amine compound is immersed in (E).

The composition ratio of this composition is 0.1 to 1000 parts by weight for (B), 50 to 2,000 parts by weight for (C) based on 100 parts by weight of (A),
(D) 0.01 to 75 parts, (E) 100 to 5000 parts by weight,
(F) is 0.5 to 100 parts by weight.

These compositions are packaged in a breathable packaging material, and used as a package together with an object to be preserved.

(Effects of the Invention) The present invention provides a composition comprising, as a main component, a mixture of an unsaturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound, and supporting a mixture of the main material and a catalyst on a carrier. To provide oxygen absorption rate,
The amount of oxygen absorbed increased, and the preservation effect of the storage object was significantly improved.

Hereinafter, the effects of the oxygen absorbing composition of the present invention will be specifically described with reference to examples.

Examples 1 to 7 (Production of Granular Composition) 0.2 g of a catalyst is dissolved or suspended in 1.0 g of a mixture of various unsaturated aliphatic hydrocarbons or an unsaturated fatty acid compound added thereto, and these are supported in a granular form. After impregnating 5 g of the body, 0.5 g of slaked lime was spread on the surface of the granular support to produce a granular composition. Table 1 shows the compositions of these compositions and the time required to reach 0.1% oxygen, the maximum amount of absorbed oxygen, and the oxygen concentration in the system over time.

Examples 8 to 10 Isoprene polymer (molecular weight 5000) using a cutter mixer
A mixture of 0.5 g and 0.5 g of soybean oil fatty acid to which an unsaturated fatty acid transition metal salt was added as a catalyst, a powdery basic substance, and a powdery carrier were uniformly mixed. This mixture was allowed to stand at 25 ° C. for 10 minutes to form a hard lump, which was pulverized with a pulverizer to produce a granular composition of about 3 mm. Table 2 shows the composition of these compositions and the time required to reach 0.1% oxygen, the maximum amount of absorbed oxygen, and the oxygen concentration in the system over time.

Example 11 0.3 g of tall oil fatty acid cobalt was added to a mixture of 0.5 g of butadiene polymer and 0.5 g of tall oil fatty acid, and the basis weight was 100 g / m ^2.
Sheet (I) impregnated into 5 × 5 cm kraft pulp sheet, and a mixture of 0.7 g glycerin (for dynamite) and 0.1 g triethanolamine impregnated into a 5 × 5 cm kraft pulp sheet having a basis weight of 100 g / m ² (II). Table 2 shows the time required until the oxygen content of the sheet composition reaches 0.1%, the maximum oxygen absorption amount, and the oxygen concentration in the system over time.

Example 12 A liquid obtained by adding 0.3 g of tall oil fatty acid cobalt to 1.0 g of a butadiene polymer (molecular weight 10,000) was impregnated into 5.0 g of a nonwoven fabric (NFR sheet RS30 manufactured by Tokuyama Corporation).
A sheet was manufactured. This sheet was packaged in a packaging material 70 × 70 mm coated with a silicone resin in the same manner as in Example 11, and the periphery was heat-sealed to produce a package. Example 13 A granular composition was produced by impregnating 5.0 g of a liquid zeolite obtained by mixing 0.3 g of a butadiene polymer (molecular weight 10,000), 0.7 tall oil fatty acid, and 0.2 g soybean oil fatty acid Co with 0.2 g. This granular composition was packaged in the silicone resin-coated packaging material 70 × 70 mm used in Example 3, and the periphery was heat-sealed to produce a package.

(Manufacture of package) The composition manufactured in Examples 1 to 10 and 2.5 g of granular calcium oxide were packed with a silicone resin-coated packaging material 70 × 70 mm with the polyethylene on the inside facing the inside and heat-sealed around. Then, a package was manufactured.

Composition sheets (I) and (II) produced in Example 11
Packaging material 70
A package was packaged in a size of × 70 mm.

The packaging material used for the production of this package is a high-quality paper of 50 g / m ^{2 on} a silicone resin monomer (SD732 manufactured by Toray Silicon Co., Ltd.).
8, a resin content of 30% toluene solution) 100 parts was dissolved in 500 parts of toluene with catalyst (Torre over silicon Co. SRX212) 0.6 parts of the solution the paper 1 m ² per 20 g (resin content 1 g / m ²⁾ coated Then, the silicone resin was polymerized at 140 ° C. for 1 minute.

Opened polyethylene (Nippon Arc Co., Ltd., Opened B type) is laminated on the opposite side of the paper coated with this silicone resin, and with this surface inside, 140 ° C, 15 kg / m ² , heat pressure of 3 seconds It is manufactured by bonding.

(Oxygen Absorption Rate) One package was sealed in a bag of vinylidene chloride-coated stretched nylon / polyethylene composite film 15 × 20 cm with 250 ml of air, and stored at 25 ° C. The time-dependent change in the oxygen concentration in the bag was measured, and the time required to reach the oxygen concentration of 0.1% was determined, which was defined as the oxygen absorption rate. The results are shown in Tables 1, 2, and 3.
And 4. After reaching an oxygen concentration of 0.1%, the system was stored as it was in an atmosphere of 40 ° C. and 100% RH, and the time-dependent change in the oxygen concentration in the system was measured. The results are shown in Tables 1, 2, 3, and 4.

(Maximum Oxygen Absorption) One package was sealed in a vinylidene chloride-coated stretched nylon / polyethylene composite film bag 25 × 30 cm with 1000 ml of air, and stored at 25 ° C. The amount of absorption determined from the decrease in oxygen concentration one month later in the bag was defined as the amount of oxygen absorption. The results are shown in Tables 1, 2, 3, and 4.

Comparative Example 1 To a mixture of 1 g of reduced iron powder of 60 mesh or less and 1 g of powdered activated carbon, 0.2 g of a 10% calcium chloride aqueous solution was uniformly added to produce a composition for absorbing oxygen. This composition was prepared in Examples 1 to
It packaged with the same packaging material and method as 7, and manufactured the oxygen absorbing composition package. The changes over time in the oxygen absorption rate, the maximum oxygen absorption amount and the oxygen concentration in the system of this package were measured in the same manner as in Examples 1 to 7. Table 3 shows the results.

Comparative Example 2 The package of Comparative Example 1 and 3 g of silica gel (type A) packaged with the same packaging material as used in Example 1 were used together with the oxygen absorption rate, the maximum oxygen absorption amount, and the oxygen in the system. The change with time of the concentration was measured in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 3 0.2 g of soybean oil fatty acid cobalt was dissolved in 1.0 g of tall oil fatty acid, impregnated with 5 g of granular zeolite, and then 0.5 g of slaked lime was dusted on the surface to produce a granular composition. This composition was packaged with the same packaging material and method as in Examples-1 to 7 to produce an oxygen-absorbing package. The changes over time in the oxygen absorption rate, the maximum oxygen absorption amount and the oxygen concentration in the system of this package were measured in the same manner as in Examples 1 to 7. Table 3 shows the results.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-67252 (JP, A) JP-A-56-155561 (JP, A) JP-A-63-198962 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B01J 20/22 A23L 3/3436

Claims (2)

(57) [Claims] An oxygen-absorbing composition comprising a mixture of an unsaturated aliphatic hydrocarbon and an unsaturated fatty acid compound as a main component, and a mixture of the main component and a catalyst carried on a carrier. 2. An oxygen-absorbing composition comprising an unsaturated aliphatic hydrocarbon as a main component and a mixture of the main component and a catalyst carried on a carrier.