JP2002336693A - Oxygen absorbent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxygen absorbent composition having both oxygen absorption activity and aldehyde absorption activity even under dry conditions and free of the generation of aldehydes even when the humidity in a system rises during storage. SOLUTION: An organic oxygen absorbent composition having oxygen absorption activity even under dry conditions and an aldehyde adsorbent containing an aldehyde adsorbing material which physically adsorbs aldehydes at low humidity and an aldehyde absorbing material which absorbs aldehydes by chemical reactions even at high humidity are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen absorbent composition having both oxygen absorption activity and aldehyde absorption activity even under dry conditions and high humidity.

[0002]

2. Description of the Related Art As an oxygen absorbent having an oxygen absorbing activity even under dry conditions, for example, an unsaturated fatty acid or an oil containing an unsaturated fatty acid is used in Japanese Patent Publication No. 62-60936, and a transition metal and its compound are contained as a catalyst. An oxygen absorber is disclosed. However, this oxygen absorbent has a problem that lower aldehyde is generated at the time of deoxygenation, which causes an unpleasant odor, and sometimes reacts with a stored article to deteriorate the stored article. Conventionally, as a means to remove aldehydes, adsorbed substances that physically adsorb aldehydes such as activated carbon and molecular sieves have been used.However, physical adsorption is limited, and humidity rise in the system due to moisture permeability during storage is limited. Sudden moisture was preferentially adsorbed, and the aldehyde that had been physically adsorbed was desorbed again, causing an unpleasant odor.

[0003] Accordingly, the inventors have disclosed Japanese Patent Application Laid-Open No. 11-2289.
No. 54 discloses an organic oxygen absorbent using an aldehyde absorbent by a chemical reaction. Although this method was an excellent invention to prevent aldehyde re-emission due to changes in ambient humidity, the absorption rate of aldehyde was slow, especially when the concentration became low, the absorption rate became extremely slow. There were still problems to be improved, such as a significant decrease in performance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to have oxygen absorption activity and aldehyde absorption activity simultaneously even under dry conditions, and to reduce the humidity in the system during storage. An object of the present invention is to provide an oxygen absorbent composition which does not cause aldehyde generation even when it rises.

[0005]

The present inventors have studied methods for solving the above-mentioned problems, and as a result, have found that an organic oxygen absorbent composition having oxygen absorption activity even under dry conditions and an aldehyde under low humidity. Aldehyde adsorbent containing an aldehyde adsorbent that physically adsorbs and an aldehyde adsorbent that absorbs aldehyde by chemical reaction even under moisture permeability (C)
Found that the purpose was achieved by using
The present invention has been completed.

That is, the present invention is an oxygen absorbent composition characterized in that it has both oxygen absorption activity and aldehyde absorption activity in a wide humidity range from drying conditions to moisture permeability conditions. Due to this composition, low-concentration aldehydes are quickly absorbed even under dry conditions, and there is no fear of unpleasant odor due to re-release.At the same time, oxygen is quickly absorbed, and aldehydes are quickly absorbed even when the humidity in the system increases during storage. An oxygen absorbing composition is provided that absorbs and does not have to worry about re-release.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aliphatic compound having an unsaturated group (A) of the present invention includes unsaturated fatty acid compounds and hydrocarbon compounds having an unsaturated group. As unsaturated fatty acid compounds, for example, linoleic acid, linolenic acid, arachidonic acid, parinaric acid, unsaturated fatty acids such as dimer acid,
And oils and fats and metal salts containing these esters. As unsaturated fatty acids, fatty acids obtained from vegetable oils and animal oils, such as linseed oil fatty acids, soybean oil fatty acids, tung oil fatty acids, bran oil fatty acids, sesame oil fatty acids, cottonseed oil fatty acids, rapeseed oil fatty acids, and tall oil fatty acids are used.

On the other hand, hydrocarbon compounds having an unsaturated group include liquid butadiene oligomer, liquid isoprene oligomer, squalene, liquid acetylene oligomer, liquid pentadiene oligomer, liquid oligoester acrylate, liquid butene oligomer, liquid BR, liquid SBR,
Liquid NBR, liquid chloroprene oligomer, liquid sulfide oligomer, liquid isobutylene oligomer, liquid butyl rubber, liquid cyclopentadiene petroleum resin, liquid oligostyrene, liquid hydroxypolyolefin oligomer, liquid alkyd resin, liquid unsaturated polyester resin, natural rubber, etc. Polymers of various molecular weights are used.

[0009] The unsaturated fatty acid compound and the hydrocarbon compound having an unsaturated group are not necessarily required to be a single substance.
It may be a mixture of two or more, or may be copolymerized. In addition, a small amount of impurities such as a solvent mixed during the production can be used in a desired range. Further, these compounds may have a substituent other than the unsaturated group. For example, alicyclic hydrocarbon group, aromatic hydrocarbon group, halogen group, hydroxyl group, hydroperoxy group, epoxy group, oxo group, carbonyl group, hydroxymethyl group, ether group, carboxyl group, ester group,
Acyl group, amino group, imino group, nitrile group, nitro group, nitroso group, amide group, imide group, cyano group, isocyano group, cyanate group, isocyanato group, diazo group,
Azide group, hydrazino group, azo group, thio group, thioxo group, mercapto group, thiocarbonyl group, sulfonyl group,
It may be substituted by a functional group such as a sulfinyl group, a sulfone group, a thiocyanato group, an isothiocyanato group, and a heterocyclic group.

The oxygen absorption promoting substance (B) of the present invention comprises C
u, Fe, Co, Ni, Cr, Mn, Ca, Pb, Zn
And at least one member selected from the group consisting of
Seeds are used. Examples thereof include inorganic salts such as sulfates, chlorides, and nitrates; organic salts such as fatty acid salts, naphthenates, rosinates, and metal salts of acetylacetone; and alkyl metal compounds. These Cu, Fe, Co, Ni, Cr,
Among Mn, Ca, Pb and compounds thereof, Fe and / or M are preferable from the viewpoint of oxygen absorption promoting performance and safety.
Salts of n and Zn are more preferred.

The carrier substance of the present invention is not particularly limited as long as it increases the contact area between an aliphatic compound having an unsaturated group containing an oxygen absorption promoting substance and oxygen, and is not particularly limited. Pulp paper and synthetic paper, non-woven fabric, porous film, silica, alumina, magnesia,
Synthetic zeolites such as titania, activated carbon and molecular sieves, natural zeolites such as mordenite and erionite, perlite, clay minerals such as activated clay, and layered compounds such as hydrotalcite are used.

The proportion of each component in the oxygen absorbent composition of the present invention is such that the metal weight is 0.001 per 100 parts by weight of the total of the aliphatic compound having an unsaturated group (A) and the oxygen absorption promoting substance (B). To 2 parts by weight, preferably 0.005 to 1
Parts by weight, more preferably in the range of 0.01 to 0.5 parts by weight, and the carrier material in the range of 1 to 1,000 parts by weight.

The amount of the aliphatic compound (A) having an unsaturated group used in the present invention is an amount necessary to keep the atmosphere in the system substantially oxygen-free at least during the storage period.
Usually, the amount is preferably 1.1 to 10 times the amount. Here, the substantially oxygen-free state means that the oxygen concentration is 5% or less, preferably 1%.
Hereinafter, it is more preferably 0.1% or less.

The adsorbing substance of the present invention which physically adsorbs aldehydes under dry conditions or low humidity conditions includes, for example, natural zeolites such as aluminum oxide, molecular sieves, mordenite, erionite, etc .; It contains clay minerals such as acid clay and activated clay, porous glass such as silica gel, activated carbon, activated carbon fiber, molecular sieve carbon, and activated carbon such as bone charcoal. These substances having an aldehyde adsorption function may be used as a carrier for the aliphatic compound (A) having an unsaturated group, or may be used by simply mixing with an oxygen absorbent. Furthermore, these aldehyde adsorbents do not necessarily have to be a single substance, but may be a mixture of two or more. Here, the drying condition or the low humidity condition means a humidity condition of 30% RH or less.

As the aldehyde-absorbing substance for chemically absorbing aldehyde of the present invention, at least one of amines, thiols and sulfonic acids is used. Here, the amines include urea compounds such as urea, thiourea and ethylene urea; hydrazine compounds, dicyandiazide and acid salts thereof; hydroxyamines such as hydroxyamine hydrochloride and hydroxyamine sulfate; guanidine phosphate, guanidine sulfamate, and hydrochloric acid Guanidine salts such as aminoguanidine; ammonium salts such as ammonium sulfate; amino alcohols such as ethanolamine; phenylamines such as aminophenol, phenylethylamine and phenylethanolamine; catecholamines such as dopamine; indoleamines such as serotonin; 2-methylimidazole;
Examples thereof include imidazoles such as 4-methylimidazole; polyamines such as putrescine; aminobenzoic acid, aminobenzene, aminomethylene, melamine, morpholine, aniline, and phenylenediamine. Examples of the thiol include alkyl mercaptan, thioglycolate, thioglycerol, thiosalicylic acid, and thiophenol. Further, as the sulfonic acid, sulfolane, sulfamic acid, thiosulfate, hypochlorite,
Sulfite, bisulfite, phenolsulfonic acid, NW acid (4-hydroxy-1-naphthalenesulfonic acid) and the like are exemplified.

The amines, thiols or sulfonic acids of the present invention include 4B acid (2-amino-5-methylbenzenesulfonic acid) and metanilic acid (m-aminobenzene), which share an amino group and a sulfo group in the molecule. Sulfonic acid), 2B acid (4-amino-2-chlorotoluene-5-
Sulfonic acid), naphthonic acid (1-naphthylamine-4)
-Sulfonic acid), tobias acid (2-aminonaphthalene-
1-sulfonic acid), sulfanilic acid (4-aminobenzenesulfonic acid), C acid (3-amino-6-chlorotoluene-4-sulfonic acid), G acid (7-hydroxynaphthalenesulfonic acid), J acid (2 -Amino-5-naphthol-
7-sulfonic acid), gamma acid (6-amino-4-hydroxy-2-naphthalenesulfonic acid), H acid (4-amino-5-hydroxy2,7-naphthalenesulfonic acid), R
Acid (2-naphthol-3,6-disulfonic acid), guanidine sulfamate, or cysteine, which shares an amino group and a mercapto group in the molecule, are more preferred because of their high aldehyde absorption ability.

The aldehyde-absorbing substance of the present invention may use amines, thiols or sulfonic acids directly. However, in order to increase the absorption rate and to improve the handling property, the amine, thiol or sulfonic acids are porous. It is more preferable to use it by supporting it on a porous material. As the porous substance, those having a large specific surface area representing the contact area with the target gas such as lower aldehyde are preferable.For example, activated carbon, activated carbon fiber, bone charcoal, activated carbon such as molecular sieve carbon, porous film, silica gel, porous Clay minerals such as porous glass, alumina, zeolite, natural zeolites such as mordenite and erionite, perlite, and activated clay are used.

The loading method is not particularly limited, and a general method is used. For example, when the substance to be loaded is a solid, it is dissolved in an aqueous solution or an organic solvent such as methanol, ethanol, acetone or the like, and then the porous material is added. The material is impregnated and mixed with the porous material, and is dried and supported at a temperature lower than the decomposition temperature, vaporization temperature, and melting temperature of the material, preferably about 50 to 100 ° C. When the substance to be supported is a liquid, the substance is supported as it is, or is diluted with an organic solvent, directly impregnated into a porous substance, mixed and supported. When the substance to be supported is a solid, the individual substances may be once ground and mixed, kneaded with an organic solvent such as water or alcohol, and then molded and fired.

Since the aldehyde is generated by the oxygen absorption reaction, the amount of the aldehyde absorbent (C) used varies depending on the amount of oxygen absorbed. However, the amines, thiols or sulfonic acids, which are the absorbing substances, are not oxidized main agents. 0.01 to 1000 parts by weight, preferably 0.1 to 100 parts by weight,
To 700 parts by weight, more preferably 1 to 400 parts by weight. When the absorbent material is supported, the ratio of the amount of the absorbent material to be supported and the amount of the porous material as the carrier is determined by the carrier 100
The load is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on parts by weight.

In the present invention, a dehumidifier can be appropriately used depending on the article to be stored. Examples of the dehumidifier include silica gel, aluminum oxide, synthetic zeolites represented by molecular sieves, natural zeolites such as mordenite and erionite, perlite, clay minerals such as acid clay and activated clay, porous glass, magnesium silicate, and aluminum silicate. , Polymer adsorbent, activated carbon, activated carbon fiber, molecular sieving carbon, bone charcoal, calcium oxide,
Calcium sulfate, calcium chloride, calcium bromide, barium oxide, barium bromide, barium perchlorate, magnesium chloride, magnesium oxide, magnesium sulfate, magnesium perchlorate, aluminum sulfate, sodium sulfate, sodium hydroxide, sodium carbonate, carbonate Potassium, potassium hydroxide, zinc chloride, zinc bromide, lithium perchlorate and the like. In addition, as the dehumidifying agent, select one that is selected as a carrier of the oxidized main agent or an aldehyde adsorbent,
It can have dehumidifying ability. Furthermore, the dehumidifier does not necessarily have to be a single substance, but may be a mixture of two or more.

In the present invention, in addition to a substance having a physical aldehyde adsorption function and an aldehyde-absorbing substance which chemically absorbs aldehyde, other additives may be used as necessary. As the additive substance, for example, CaO,
Silica gel can be used, and they are used alone or in combination in the form of powder, granules, tablets or sheets. It is not preferable that the oxygen absorbent composition of the present invention directly touches an object to be stored, and is usually used by being wrapped in a gas-permeable packaging material made of paper, nonwoven fabric, plastic or the like. The form of the package can be freely selected according to the purpose, such as a small bag, a sheet, a blister package, or the like.

The package of the oxygen-absorbing composition of the present invention can be stored under dry or low humidity conditions, for example, metal parts, electronic parts, electric parts, precision parts, magnetic / optical parts,
Jewelry, weapons, aircraft, automobiles, glass, rubber products,
Photographic film, food, medicine, pressed flowers, paintings, ancient documents,
It is suitably used for storing excavated items.

[0023]

EXAMPLES Examples of the present invention will be shown below, and will be described more specifically. Note that the present invention is not limited to these examples.

The silicon oxide deposited PET used in the examples
The laminated film pouch was prepared as follows. A 50 μm LLDPE film was laminated by dry lamination on the silicon oxide deposition surface side of the silicon oxide deposition film [MOS-TB manufactured by Oike Industry Co., Ltd.]. LLD of this film
Heat-sealed on three sides with PE surface inside, size 22
A bag of 0 mm x 300 mm was manufactured.

Example 1 Tall oil fatty acid was selected as an aliphatic compound having an unsaturated group, and tall oil fatty acid cobalt was selected as an oxygen absorption promoting substance.
00 g and 2.5 g of tall oil fatty acid cobalt are mixed to form a uniform liquid. 102.5 g of this liquid to be oxidized was impregnated and mixed with 400 g of molecular sieves 13X which had been dried using a dryer at 150 ° C. for 2 hours to prepare a composition.
Next, 15 g of metanilic acid was dissolved in methanol, impregnated in 200 g of sepiolite, mixed, and dried at 120 ° C.
After removing the methanol, an aldehyde absorbent (C) was prepared. Subsequently, 5.03 g of the above composition and an aldehyde absorbent (B) 2.15, which is a chemical aldehyde absorbent, were used.
g, mixed with 1.0 g of quicklime as a dehumidifier, and laminated with a polyethylene film having an opening on the inner surface, 45 mm x 9
It was filled in a small bag of paper of 0 mm, and the periphery was heat-sealed to produce an oxygen absorbent composition package.

The obtained package of the oxygen absorbent composition was charged with 25
Sealed in a silicon oxide vapor deposited film bag together with 300 ml of air at 60 ° C. and 60% RH, stored in an atmosphere of 25 ° C. and 60% RH, and analyzed the oxygen concentration and relative humidity in the bag over time with a gas chromatograph. Use a commercially available gas detector tube (Gastech: formaldehyde detector tube 91)
L). The results are shown in Table 1. as a result,
The oxygen concentration was 0.1% or less after 1 day and 3 months of storage. Further, the formaldehyde concentration was below the lower limit of detection (0.5 ppm) after 1 day and after storage for 3 months.

<Example 2> The tall oil fatty acid of Example 1 was replaced with a liquid polyisoprene oligomer,
Co was replaced by Co naphthenate. In addition, activated carbon was used as a physical aldehyde absorbent for the aldehyde absorbent (C) in an amount of 0.5
g was performed in the same manner as in Example 1 except that g was added and metanilic acid was replaced with sulfanilic acid. The results are shown in Table 1. As a result, after one day and three months, the oxygen concentration was 0.1%.
% And formaldehyde was below the lower limit of detection.

Example 3 The tall oil fatty acid of Example 1 was changed to a mixture of a tall oil fatty acid and a liquid polyisoprene oligomer (weight ratio 6: 4), the tall oil fatty acid Co was changed to Fe naphthenate, and the carrier substance was changed. To molecular sieves 13
X was replaced with natural zeolite (mordenite). Also, 0.5 g of activated carbon was added as a physical aldehyde absorbent of the aldehyde absorbent (C), metanilic acid was replaced with naphthonic acid, sepiolite as a carrier was replaced with activated carbon, and quicklime, which was another added substance, was replaced with silica gel 1. The procedure was performed in the same manner as in Example 1 except that the amount was changed to 0 g. Table 1 shows the results
It was shown to. As a result, the oxygen concentration was reduced to 0.1% or less after 1 day and 3 months, and the formaldehyde was also below the detection lower limit.

Example 4 The tall oil fatty acid of Example 1 was replaced with a liquid polybutadiene oligomer,
Co was changed to tall oil fatty acid Mn, and the carrier substance was changed from molecular sieves 13X to natural zeolite (mordenite). Further, 0.5 g of activated carbon was added as a physical aldehyde absorbent of the aldehyde absorbent (C), metanilic acid was changed to morpholine, sepiolite as a carrier was changed to activated carbon, and quicklime, which was another added substance, was changed to silica gel 1.
The procedure was performed in the same manner as in Example 1 except that the amount was changed to 0 g.
The results are shown in Table 1. As a result, the oxygen concentration was reduced to 0.1% or less after 1 day and 3 months, and the formaldehyde was also below the detection lower limit.

Example 5 The tall oil fatty acid of Example 1 was changed to soybean oil, the tall oil fatty acid Co was changed to naphthenic acid Mn, and the carrier substance was changed from molecular sieves 13X to natural zeolite (mordenite). Further, the same procedure as in Example 1 was carried out except that the metanylic acid of the aldehyde absorbent (C) was changed to ethylene urea and quicklime, which was another additive substance, was not added. The results are shown in Table 1. As a result, the oxygen concentration was reduced to 0.1% or less after 1 day and 3 months, and the formaldehyde was also below the detection lower limit.

<Comparative Example 1> The procedure of Example 1 was repeated, except that sepiolite, which was the chemical aldehyde absorbent of Example 1, impregnated with metanilic acid was not used. The results are shown in Table 2. As a result, after storage for one day, it was the same as Example 1, but after storage for three months, formaldehyde was 9 pp
m was detected.

<Comparative Example 2> The procedure of Example 2 was repeated except that sepiolite, a chemical aldehyde absorbent of Example 2, impregnated with sulfanilic acid was not used. The results are shown in Table 2. As a result, after storage for one day, the result was the same as that of Example 1, but after storage for three months, the amount of formaldehyde was 8%.
ppm was detected.

<Comparative Example 3> The procedure of Example 1 was repeated, except that the carrier material of Example 1 was changed from molecular sieves 13X to diatomaceous earth. The results are shown in Table 2. As a result, 1
After storage for 7 days, 7 ppm of formaldehyde was detected.

<Comparative Example 4> The procedure of Example 3 was repeated, except that the carrier material in Example 3 was changed from natural zeolite to diatomaceous earth. The results are shown in Table 2. As a result, 5 ppm of formaldehyde was detected after storage for one day.

<Comparative Example 5> The procedure of Example 4 was repeated, except that the oxygen absorption-promoting substance of the aliphatic compound (A) having an unsaturated group was not added. The results are shown in Table 2. As a result, the oxygen concentration after storage for one day was 20.9%,
It was 20.5% after storage for months.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

According to the present invention, under dry conditions or low humidity conditions, a composition containing an aldehyde absorbent having aldehyde absorption activity physically and chemically simultaneously with an oxygen absorbent composition having oxygen absorption activity can be used. Concentrated aldehydes are quickly absorbed and there is no fear of off-flavors due to re-emission, and oxygen is absorbed quickly, realizing an oxygen-absorbing composition that is free from aldehyde re-generation and off-flavors even when the humidity in the system increases. it can.

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Tatsuo Iwai 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Plant F-term (reference) 4C080 AA05 AA06 BB02 BB04 CC02 HH05 JJ03 KK08 LL03 LL10 MM17 MM18 4G066 AA05B AA61B AB01B AB09B AB15B AB23D AB29B AD03B AD04B AD10B BA12 BA36 CA37 CA52 DA03 FA12 FA21

Claims (6)

[Claims] 1. An oxygen absorbent composition comprising: an aliphatic compound having an unsaturated group (A); an oxygen absorption promoting substance (B); and an aldehyde absorbent (C) having aldehyde absorption activity. . 2. The method according to claim 1, wherein the oxygen absorption promoting substance (B) is Cu, Fe,
The oxygen absorbent composition according to claim 1, comprising at least one selected from Co, Ni, Cr, Mn, Ca, Pb, Zn, and these compounds. 3. The oxygen absorbent composition according to claim 1, wherein the aldehyde absorbent (C) is an aldehyde adsorbent which physically adsorbs aldehyde under low humidity and a substance which absorbs aldehyde by a chemical reaction. 4. The oxygen absorbent composition according to claim 3, wherein the substance that absorbs aldehyde by a chemical reaction contains at least one of amine, thiol, and sulfonic acid. 5. An amine, thiol or sulfonic acid,
The oxygen absorbent composition according to claim 4, comprising at least one of metanilic acid, naphthionic acid, tobiasic acid, sulfanilic acid, and cysteine, which shares at least two amino groups, mercapto groups, or sulfo groups in the molecule. . 6. The method of claim 1, wherein the amine is morpholine, piperidine,
The oxygen absorbent composition according to claim 5, comprising at least one selected from piperazine and ethylene urea.