JPH1170331A - Deoxygenation component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery or granular deoxidizing component having excellent deoxidizing performance, which can be used even in a dry state. SOLUTION: It is a powdery or granular deoxidizing component having an average particle size of 0.01 to 5 mm, comprising a crosslinked polymer having a carbon-carbon unsaturated bond. It has high heat resistance and easy pulverizability by introducing a crosslinked structure, and can be applied to a wide range of applications.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery or granular deoxidizing component having excellent deoxidizing performance and usable in a wide humidity range from a dry state to a high humidity state. The deoxidizing component of the present invention, as it is or by mixing an adsorbent or the like, in a form put in a small bag, in a form kneaded in a resin, in a form of a container and a package kneaded in a resin, and the like,
It is used for the purpose of preventing the oxidation of various articles which are easily deteriorated under the influence of oxygen, such as foods, pharmaceuticals, metal products and electronic products.

[0002]

2. Description of the Related Art For the purpose of preventing the oxidation of various articles, such as foods, pharmaceuticals, metal products and electronic products, which are susceptible to deterioration under the influence of oxygen, oxygen contained in a packaging container or a packaging bag containing them is used. Deoxidizers for removal have been used in the past. A form which was initially developed as an oxygen absorber and is still widely used is a powder or granular oxygen-absorbing component packed in a small bag. In addition, as a safe oxygen absorber that is easier to handle and has a wider application range, and has no problems such as accidental eating, the shape of a single-layer or multilayer film or sheet including a layer made of a resin into which an oxygen-absorbing component is kneaded is considered. There is something.

At present, iron powder is most frequently used as a deoxidizing component. However, in order to oxidize metal powder such as iron powder, moisture is required, and if the system to be deoxidized has a small amount of moisture (hereinafter referred to as a drying system), is there any possibility that deoxidation will occur? Or the speed was very low. On the other hand, a reaction system in which various organic compounds are oxidized has been developed as a deoxidizing component that can be used not only in a high-humidity system but also in a dry system. As an example of this deoxygenation component,
In the case of those containing an unsaturated carbon-carbon bond, a low molecular weight system (JP-B-60-28266, JP-B-62-60936, etc.) or a polymer system (JP-A-4-29741, JP-A-5-115)
776) and low molecular weight compounds such as alcohols (JP-A-3-8441, etc.) or polyolefins (JP-A-4-187, etc.) which contain almost no unsaturated carbon-carbon bond.
238), ethylene-vinyl alcohol copolymer (for example, Japanese Patent Publication No. 6-49354), polyvinyl chloride (for example, JP-A-3-269044), polyamide (for example,
00846), each of which contains various metals or metal compounds as catalysts for promoting the reaction with oxygen.

On the other hand, when these deoxidizing components for a drying system are actually used, it is desirable that they be solids that can be easily handled. Further, as in a general solid state reaction, it is desirable to increase the surface area of the solid to speed up the oxidation reaction. From this viewpoint, examples of obtaining a powdery or granular solid include a system for supporting or solidifying a low molecule (liquid) on a carrier (Japanese Patent Publication No. 62-60936, Japanese Patent Publication No. 8-11056, etc.), a polymer (solid) System for crushing lump (Japanese Patent Laid-Open No. 4-1)
87238). However, when carrying or solidifying a liquid, there is a risk of leakage of the liquid, and when pulverizing a solid mass, the various polymers (thermoplastic resins) are flexible near room temperature. Therefore, it was necessary to pulverize at a low temperature. Further, in some polymer systems having an unsaturated carbon-carbon bond, particularly having a low glass transition temperature, even if the powder is once pulverized at a low temperature, the powder or particles re-attach to each other when the temperature is returned to around room temperature. Therefore, there was a problem that it became a large lump.

As described above, deoxidizing components for a drying system have been already known, but there has been no powdery or granular material which is easy to handle and has all of its components solid.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to provide excellent deoxygenation performance, to be usable in a wide humidity range from a dry state to a high humidity state, and to be easy to handle. It is to provide a powdery or granular deoxygenation component.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by introducing an appropriate cross-linking structure into an organic compound having a carbon-carbon unsaturated bond, powdery or granular cross-linking that is easy to handle is achieved. The present inventors have found that they can be used as a deoxidizing component composed of a polymer and at the same time exhibit excellent deoxidizing performance, and thus completed the present invention.

[0008] The present invention relates to a deoxygenating component comprising a crosslinked polymer having a carbon-carbon unsaturated bond in a powdery or granular form having an average particle size of 0.01 to 5 mm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The crosslinked polymer in the present invention is
A polymer compound having a carbon-carbon unsaturated bond and a crosslinking point in a molecule. The crosslink in the present invention refers to a crosslink consisting of a covalent bond. In this case, various covalent bonds can be used, but in order to impart heat resistance to the crosslinked polymer,
A crosslinked structure by a bond having a high binding energy such as CC, CO, CN is desirable. By introducing such a crosslinked structure, the molecules become large and become insoluble and infusible,
It becomes an easy-to-handle deoxygenation component, and its application range expands.
In addition, since a carrier or the like is not required, the amount of oxygen absorbed per unit weight increases.

Various methods known in polymer chemistry can be used for the production of the crosslinked polymer in the present invention. For example, a crosslinked polymer can be obtained by directly polymerizing a single or plural types of monomers having a relatively small molecular weight (including some of which have three or more functional groups, and having a total average functional group of more than 2). Alternatively, a crosslinked polymer may be obtained by later crosslinking an oligomer or polymer having a relatively large molecular weight. Of these, the latter method, which generates less heat of polymerization and is suitable for mass production, is suitable. As a method for performing crosslinking later, it is possible to use ordinary physical or chemical means. Physical crosslinking methods include simple high-temperature heating, irradiation with electromagnetic waves (ultraviolet rays, γ rays, microwaves, etc.), particle beams (electrons, etc.), and ultrasonic waves. Chemical crosslinking methods include And a method using a reaction using various radical generators known as an initiator or a crosslinking agent. Among them, a method by a crosslinking reaction using an organic peroxide as a radical generator is desirable. A specific method for producing a powdery or granular crosslinked polymer using chemical crosslinking is as follows. That is, first, the mixture of the organic compound (substance to be crosslinked) and the radical generator before crosslinking is crosslinked in a lump state, crosslinked in a solution state, crosslinked in a suspension state or an emulsified state, or the like. I do. Thereafter, in order to make a powdery or granular solid, if the crosslinking in a lump state, crushing,
In the case of crosslinking in a solution state, drying and pulverization are performed, and in the case of crosslinking in a suspension state or emulsification state, separation and drying of a liquid phase are performed. For each of these unit operations, various methods and apparatuses known from chemical engineering can be used.

The crosslinked polymer in the present invention must be in the form of powder or granules having an average particle size of 0.01 to 5 mm. If the particle size is too large, the oxygen absorption rate will be too low,
If the particle size is too small, there is a danger such as dust explosion. A more desirable range of the particle size is 0.03 to 0.5 mm.

The degree of cross-linking in the cross-linked polymer in the present invention must be set within such a range that powder or granules can be easily obtained and at the same time, appropriate heat resistance and oxygen absorption performance can be obtained. The appropriate degree of cross-linking varies depending on the molecular structure and molecular weight of the object to be cross-linked, but preferably contains 0.0001 to 0.02 mol of cross-linking points per gram of cross-linked polymer. As a result, for example, in the case of pulverization after cross-linking in a lump state, the plasticity of the cross-linked polymer is reduced due to appropriate cross-linking, and the cross-linked polymer becomes brittle to facilitate pulverization.

As a change in physical properties due to crosslinking, the crosslinked polymer of the present invention has a flexural modulus at 25 ° C. of 0.1.
It is preferably at least MPa, more preferably at least 1 MPa, even more preferably at least 10 MPa. Further, the crosslinked polymer in the present invention preferably has a bending strength (breaking strength) at 25 ° C. of at least 100 MPa or less, more preferably 10 MPa or less. Further, the crosslinked polymer in the present invention preferably has a linear expansion (increase in one direction) of 50% or less after immersion in toluene at 25 ° C. for one day.

Regarding the relationship between the heat resistance and the degree of crosslinking, when the powder or granules are used as an oxygen scavenger, they are kneaded in a resin up to 100 ° C. or higher, preferably 150 ° C. or higher, and used in various forms. In some cases, the crosslinking is carried out up to 150 ° C. or more, preferably up to 200 ° C. or more so as not to flow or adhere to each other. This makes it possible to keep the deoxidizing component in a solid state in each use form, and as in the case of iron powder, a single layer or a multilayer including a layer made of a resin into which the deoxidizing agent or the deoxidizing component is kneaded. Of a film or sheet in the form of a deoxidizer.

In relation to the oxygen absorption performance and the degree of crosslinking,
When an organic compound containing a carbon-carbon unsaturated bond is used for the object to be crosslinked, the same bond (precisely, the carbon having the same bond and the carbon adjacent thereto) mainly participates in the crosslinking, but the same bond reacts with oxygen. Therefore, it is necessary to leave the bond appropriately. Specifically, an organic compound containing a plurality of carbon-carbon unsaturated bonds in one molecule is used, cross-linking is performed using only a part of the bonds, and 0.001 to 0.025 m / g after cross-linking.
It is preferred to leave a carbon-carbon unsaturated bond of ol.

In the deoxidizing component of the present invention, various kinds of metals or metal compounds are added as a catalyst and the oxidation reaction of the deoxidizing component is not added, as is known in ordinary autoxidation of organic compounds. Can also be promoted. However, even if the particle size is reduced, the reactivity is increased. Therefore, if the particle size is sufficiently reduced, an appropriate oxidation rate can be obtained without adding this catalyst. Also, in general, the smaller the particle size, the less the catalyst may be. Further, when various polymers are used as the object to be crosslinked, there is a possibility that an effective oxidation catalyst may be obtained with only a small amount of the remaining polymerization catalyst. The metal used in the catalyst or the metal species in the metal compound is not particularly limited, but a transition metal is particularly desirable because its electronic state is for a catalyst. Of these metal species, cobalt is known to exhibit particularly high catalytic activity, and iron and manganese are known to be relatively safe. The catalyst in the present invention is mixed with the object to be cross-linked before cross-linking, particularly in the case of chemical cross-linking, with the object to be cross-linked and a radical generator. As a result, the catalyst is uniformly dispersed or dissolved, and is uniformly contained even after crosslinking. Here, it is desirable to use a catalyst having high solubility in the organic compound to be crosslinked so that the catalyst can be more uniformly dispersed or dissolved. Specific examples include metal fatty acid salts. In that case, if the fatty acid portion contains a carbon-carbon unsaturated bond, it can be incorporated into a crosslinked polymer. Since the catalyst in the deoxygenated component is taken into the crosslinked structure, the catalyst rarely leaks from the deoxygenated component. As a result, even when this deoxygenated component is used by being kneaded into a thermoplastic resin serving as a matrix component,
Since the catalyst is unlikely to leak out of the deoxygenated component, degradation due to oxidation of the matrix component is minimized.

In the deoxygenating component of the present invention, the oxidation reaction is also promoted by irradiation with light (mainly in the ultraviolet region), as is also known in autoxidation. However, irradiation of light is not essential because the powder or the particles are small, and when a catalyst is further added, the catalyst also acts.

As the object to be crosslinked, a compound containing a carbon-carbon unsaturated bond is used. As the compound having a large number of carbon-carbon unsaturated bonds contained per unit weight, a polymer (oligomer, polymer or copolymer) of a diene compound is particularly preferable, and specific examples thereof include polybutadiene and polyisoprene.

Incidentally, in the polymer of the diene compound, an antioxidant is often added. It is desirable that such an antioxidant is not contained because it prevents deoxidation after cross-linking to form a deoxygenated product. It can also be activated.

The safety against accidental eating of the deoxygenated component according to the present invention is extremely high. This is because, as a crosslinked product, the solubility of the powder or the whole as a whole is extremely low, and the elution of the low-molecular compound or the metal of the catalyst generated by the oxidation from the individual powder or the particle is extremely small. That's why.

In general, in the case of a deoxidizing agent containing an organic compound as a main component, a low molecular weight compound which emits an odor is generated with the oxidation reaction. However, the crosslinked polymer in the present invention is
Due to tight internal bonds, low-molecular-weight compounds are less generated,
Further, the release (volatilization and elution) of the low molecular compound out of the powder or the granules is small. In addition, since the increase in volume during the oxidation reaction is limited by the crosslinked structure, the oxidation reaction does not proceed too much, and the production of low molecular weight compounds is reduced. As a further improvement in odor, first, there is an improvement in the molecular structure of the oxide target. This corresponds to a structure which is not eliminated as a low molecular compound even if a covalent bond is broken by an oxidation reaction. Specifically, for example, in the case of oligomers and polymers of diene compounds, use of a variety having a small side chain and a low ratio of 1,2 bonds,
Also, the use of polybutadiene is recommended over polyisoprene. In addition, although the oxygen absorption performance is low, it is also effective to use a copolymer of a diene and an olefin containing a carbon-carbon unsaturated bond loosely, an oligomer of a diene compound or a partially hydrogenated product of a polymer. is there. In chemical cross-linking, there are low-molecular compounds derived from radical generators, and for this too, select molecules with the largest possible size after radical cleavage, or select the same as small as possible and remove them after crosslinking. Thereby, generation of odor is reduced. On the other hand, as a method of removing the odor that cannot be avoided after oxidation, an adsorbent such as activated carbon may be used together with the deoxidizing component.

The oxygen scavenger of the present invention is a main component of the oxygen scavenger, and is used not only alone but also as a desiccant,
It can be used together with an adsorbent, an antibacterial agent and the like.

The deoxidizing component of the present invention may be used as a deoxidizing agent in the form of powder or granules and placed in a gas-permeable small bag, and may be kneaded and stretched in a thermoplastic resin into small pieces to form small pieces. Used as a deoxidizer in the form of labels, cards, packing, etc., and kneaded in a thermoplastic resin as a deoxidizing packaging material such as a film or sheet. And the like. FIG. 1 shows a form in which a deoxygenated component is placed in a breathable pouch. FIG. 2 shows a form in which a small piece kneaded into a thermoplastic resin and stretched is used as a label. FIG. 3 shows a form in which the resin is kneaded into a thermoplastic resin to form a part of a packaging container.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The compounds used are as follows. Crosslinked product, butadiene oligomer: manufactured by Zeon Corporation, trade name Polyoil 110, average molecular weight 1600, 1,4 structure 99
%, A liquid having a viscosity of 750 cP at 20 ° C., and a trade name
Polyoil 130, average molecular weight 3000, 1,4 structure 99
%, A liquid having a viscosity of 3000 cP at 20 ° C. In both cases, the number of carbon-carbon double bonds is
It is calculated as 1/54 = 0.0185 mol / g. Crosslinked product, polyisoprene: manufactured by Nippon Synthetic Rubber Co., Ltd., trade name IR 2200, 1,4 structure 98%, average molecular weight about 1
0 ^6, carbon - number of carbon double bonds molecular weight of the monomer 68
From this, it is calculated as 1/68 = 0.0147 mol / g. 2
The flexural modulus at 5 ° C. was 1.0 MPa (measured by a method described later). Crosslinked product, styrene-butadiene copolymer: manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: E-SBR 1500, bound styrene 23.5
% Random copolymer, molecular weight of about 4 × 10 ⁵ , and the number of carbon-carbon double bonds derived from butadiene is (1-0.235)
/54=0.0142 mol / g is calculated. The elastic modulus at 25 ° C. was 1.1 MPa (measured by a method described later). Organic peroxide, α, α'-bis (tert-butylperoxy) diisopr
opylbenzene: manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perbutyl P, molecular weight: 338, effective functional groups per mol: 2 mo
l, 95% purity. Catalyst, cobalt stearate: Mitsuwa Chemicals Co., Ltd.
98% purity. Catalyst, tall oil fatty acid manganese: Toei Kako Co., Ltd., purity about 97%. Catalyst, iron (III) stearate: Mitsuwa Chemical Co., Ltd., purity 95% or more. Adsorbent and activated carbon: Takeda Pharmaceutical Co., Ltd., Shirasagi A, sieved and used at 50 μm or more.

The methods for measuring various properties are as follows. The flexural modulus and flexural strength of the deoxidized component can be determined by cutting a test piece (for example, about 4 cm x 1 cm x 2 mm) from the crosslinked product before pulverization.
It was measured by performing a three-point bending test at 5 ° C. At this time, when the bending elastic modulus E is given a relatively small deformation,
Equation: E = FL ³ / 4WT ³ D, and bending strength S is given by equation: S =
Using 3FL / 2WT ^2, it was calculated, respectively. Here, F is the load, L is the span, W is the width of the test piece, T is the thickness of the test piece, D is the displacement (deflection) (JIS K).
7203 (1995)). The deformation speed is about 10cm / s
And The linear expansion (increase ratio) due to the swelling of the deoxygenated component is determined by cutting a test piece (about 5 cm in length and 2 mm or less in thickness) from the crosslinked product before pulverization, and toluene (special grade, test piece) at 25 ° C. (Using a volume of about 100 times) for one day, and the length change before and after the immersion was divided by the dimension before the immersion to obtain the value. In addition, all the samples described below reached swelling equilibrium within 6 hours. The density of the deoxygenation component is ethanol (special grade)
Was measured at 25 ° C. using a pycnometer.

The degree of crosslinking of the deoxygenated component is determined by the following equation: ν = − (v + μv ² + log _e (1-)
v)) / (ρV _o (v ^1/3 −v / 2)) + 2 / M was estimated (Junji Furukawa, Shinzo Yamashita, The Society of Rubber Industry, Japan, 30,955 (1957)). Here, v is the fraction of the volume before swelling relative to the volume after swelling, and the linear expansion due to swelling (ratio of increase, measured as described above) is α, and v = 1 / (1+
α) ³ ; μ; interaction parameter between a macromolecule (here, a crosslinked product) and a solvent (a value for each target system described later is, for example, RGBeaman, J. Polymer Sci., 9,470 (195
2)), ρ; density of crosslinked product (measured as described above),
V _o ; molecular volume of the solvent (107 cm ³ /
mol), M: molecular weight of the object to be crosslinked before crosslinking. From ν obtained from this, the number of crosslinking points is calculated to be と of ν. The number of carbon-carbon double bonds in the cross-linked product is partially used by the cross-linking reaction (however, in general, not all of the cross-linking reaction component is derived from the same bond).
The calculation was performed on the assumption that the number was equal to the number of the same bonds before crosslinking minus the number of crosslinking points.

The heat resistance of the deoxidizing component is determined by placing a powder or granules on a metal plate heated to a predetermined temperature for about 30 seconds (for a long time, there is deformation or discoloration due to oxidation, etc.), Was determined by observing the adhesion. The oxygen absorption performance of the deoxygenated component was measured by placing 1 g of the deoxygenated component sieved to a diameter of 300 μm or less and 1000 cm ³ of air in a transparent oxygen barrier bag containing a nylon layer coated with polyvinylidene chloride. The change over time in the oxygen concentration at 25 ° C. was monitored by gas chromatography. The odor was judged sensorially by smelling the gas inside the bag.

Example 1 Butadiene oligomer (Polyoil 110); 90 parts by weight,
Perbutyl P; 10 parts by weight, cobalt stearate;
After mixing 0.1 parts by weight at about 60 ° C., the mixture was heated at 180 ° C. for 10 minutes in a container purged with nitrogen to obtain a crosslinked product. This was cooled to room temperature and then taken out. A part was used as a sample for measurement, and the other was pulverized with a rotary blade type pulverizer, mortar and pestle to form a powder. Since the crosslinked product was brittle, grinding was extremely easy. According to various measurements, the crosslinked polymer had a flexural modulus of 2.7 MPa, a flexural strength of 1.0 MPa, and a specific gravity of 0.96 g / c.
m ³ , the linear expansion due to swelling during immersion in toluene was 30%. Using μ = 0.37, ν = 0.0026 mol / g,
The number of crosslinking points was calculated to be 0.0013 mol / g. Also,
The number of carbon-carbon double bonds in the crosslinked product is 0.0185 ×
(90 / 100.1) -0.0013 = 0.0153mo
l / g was calculated. The heat resistance was 150 ° C. or higher. FIG. 4 shows how oxygen is absorbed. When oxygen was absorbed by adding 0.5 g of activated carbon to 1 g of the deoxidized component, almost no odor was felt.

Example 2 A powdery crosslinked product was obtained in the same manner as in Example 1 except that manganese tall oil fatty acid; 0.1 part by weight was used instead of cobalt stearate. FIG. 4 shows how oxygen is absorbed.

Example 3 A powdery crosslinked polymer containing no catalyst was obtained in the same manner as in Example 1 except that cobalt stearate was not used.
FIG. 4 shows how oxygen is absorbed. In this example, the induction period of particularly slow oxygen absorption is longer than that of Example 1 or Example 2,
Considering this example in combination with Example 1 or Example 2, it can be seen that the induction period can be adjusted by the addition ratio of the catalyst.

Example 4 Butadiene oligomer (Polyoil 130): 93 parts by weight,
Perbutyl P; 7 parts by weight, iron (III) stearate; 1
A powdery crosslinked product was obtained in the same manner as in Example 1 except that the weight part was used. From various measurements, the flexural modulus of the crosslinked polymer was 2.8 MPa, the flexural strength was 1.0 MPa, and the specific gravity was 0.95 g / c.
The linear expansion due to swelling at m ³ and toluene immersion was 32%. Using μ = 0.37, ν = 0.0019 mol / g,
The number of crosslinking points was calculated to be 0.0010 mol / g. Also,
The number of carbon-carbon double bonds in the crosslinked product is 0.0185 ×
(93/101) -0.0010 = 0.0160 mol / g
It was calculated. The heat resistance was 150 ° C. or higher.
FIG. 4 shows how oxygen is absorbed. When oxygen was absorbed by adding 0.5 g of activated carbon to 1 g of the deoxidized component, almost no odor was felt.

EXAMPLE 5 87 parts by weight of polyisoprene (IR 2200), 11 parts by weight of perbutyl P, and 2 parts by weight of manganese tall oil fatty acid were mixed at about 90 ° C., and then mixed between two metal plates of a heating press. And sandwiched between two polyethylene terephthalate sheets (to prevent the press from adhering to the metal plate) at 170.degree.
After heating for a minute, a crosslinked polymer was obtained. This sheet was taken out together with the sheet, cooled to room temperature, and then taken out. A part of the sheet was used as a sample for measurement, and the other part was pulverized with a rotary blade type pulverizer, mortar and pestle to form a powder. The crosslinked product was slightly rubbery, but could be ground. According to various measurements, the flexural modulus of the crosslinked polymer was 4.6 MPa, and the flexural strength was 0.8 MPa.
a, the specific gravity was 0.97 g / cm ³ , and the linear expansion due to swelling upon immersion in toluene was 24%. Using μ = 0.39, ν =
0.0020 mol / g, the number of crosslinking points is 0.0010 mol / g
It was calculated. The number of carbon-carbon double bonds in the crosslinked product is 0.0147 × (87/100) −0.0010 =
It was calculated to be 0.0118 mol / g. Heat resistance is 15
It was 0 ° C or higher. FIG. 4 shows how oxygen is absorbed. When oxygen was absorbed by adding 0.5 g of activated carbon to 1 g of the deoxidized component, almost no odor was felt.

Example 6 93 parts by weight of a styrene-butadiene copolymer (E-SBR 1500); 5 parts by weight of perbutyl P; and 2 parts by weight of manganese tall oil fatty acid were mixed at about 90 ° C. Similarly 1
After heating at 70 ° C. for 5 minutes to obtain a crosslinked polymer, a part thereof was used as a sample for measurement, and the other was pulverized into a powder. The crosslinked polymer was slightly rubbery but pulverizable. According to various measurements, the elastic modulus of the crosslinked product was 21 MPa, the bending strength was 2.4 MPa, the specific gravity was 0.98 g / cm ³ , and the linear expansion due to swelling upon immersion in toluene was 20%. Using μ = 0.31, ν = 0.0032 mol / g, and the number of crosslinking points is 0.001.
It was estimated to be 6 mol / g. The number of carbon-carbon double bonds in the crosslinked product is 0.0142 × (93/100) −0.0
016 was calculated to be 0.0116 mol / g. The heat resistance was 150 ° C. or higher. FIG. 4 shows how oxygen is absorbed. When oxygen was absorbed by adding 0.5 g of activated carbon to 1 g of the deoxidized component, almost no odor was felt.

Comparative Example 1 0.1 part by weight of cobalt stearate was dissolved at about 60 ° C. in 100 parts by weight of a butadiene oligomer (Polyoil 110). This solution was a viscous liquid, and it was difficult to use it as a stable deoxygenating component.

Comparative Example 2 100 parts by weight of polyisoprene (IR 2200) and 0.1 part by weight of tall oil manganese fatty acid were mixed at 90 ° C., cooled to room temperature, and then pulverized. This mixture was rubbery and soft, and was difficult to pulverize at room temperature. In addition, when pulverized by cooling with liquid nitrogen, pulverization was possible. However, when the temperature was returned to room temperature, the powders adhered to each other, and it was difficult to use as a stable deoxygenation component as it was.

[0036]

The deoxidizing component of the present invention can be used in a wide humidity range from a dry state to a high humidity state,
Not only high oxygen absorption rate, but also high safety against accidental eating. This oxygen-absorbing component is used for various purposes such as oxygen absorbers, oxygen-absorbing films and sheets, etc., for the purpose of preventing the oxidation of various articles that are easily affected by oxygen, such as foods, pharmaceuticals, metal products and electronic products. It can be used to construct a deoxidizer.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a form in which a deoxygenating component is placed in a breathable pouch.

FIG. 2 is a sectional view of a form in which a small piece obtained by kneading a deoxygenated component into a thermoplastic resin and stretching is used as a label.

FIG. 3 is a cross-sectional view of a form in which a deoxidized component is kneaded into a thermoplastic resin and used as a single layer to form a packaging container.

FIG. 4 is a time-dependent change in the amount of oxygen absorbed by the deoxygenated components in Examples 1 to 5.

[Explanation of symbols]

DESCRIPTION OF REFERENCE NUMERALS 1 deoxidizing component (crosslinked polymer according to the present invention) 2 air-permeable film (single layer or multilayer) 3 small piece obtained by kneading and stretching oxygen absorbing component (crosslinked polymer according to the present invention) into a thermoplastic resin 4 surface on one side (Here in the lower part of the figure) a sticky sheet 5 an oxygen-permeable and nonporous resin layer 6 a deoxygenation layer in which a deoxygenation component (crosslinked polymer according to the present invention) is kneaded in a thermoplastic resin 7 a barrier Layer (single or multilayer)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Noriyuki Kimura, Inventor 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory

Claims (7)

[Claims] 1. An oxygen-absorbing component comprising a crosslinked polymer having an average particle size of 0.01 to 5 mm and having a powdery or granular shape and having a carbon-carbon unsaturated bond. 2. The method according to claim 1, wherein the crosslinked polymer has a content of 0.001 to 1 g.
2. The deoxygenation component according to claim 1, which has 0.025 mol of carbon-carbon unsaturated bonds and 0.0001 to 0.02 mol of crosslinking points per gram. 3. The deoxygenation method according to claim 1, wherein the crosslinked polymer is a polymer obtained by partially crosslinking a diene polymer or a copolymer of a diene and another unsaturated compound. component. 4. A crosslinked polymer comprising one of a metal or a metal compound that catalyzes an oxidation reaction and a compound that prevents electrification.
The deoxidizing component according to any one of claims 1 to 3, wherein the component contains at least one component. 5. A cross-linked polymer having a flexural modulus at 25 ° C. of 0.1 MPa or more.
A deoxidizing component according to any one of the above. 6. The deoxidizing component according to claim 1, wherein the crosslinked polymer has a flexural strength at 25 ° C. of 100 MPa or less. 7. The deoxygenation method according to claim 1, wherein the cross-linked polymer has a linear expansion of 50% or less after being swelled by immersion in toluene at 25 ° C. for one day. component.