JPH09313928A - Antioxidant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antioxidant useful as an oxygen and/or halogen catching agent, a resin compsn. containing the oxidation inhibitor and excellent in oxidation resistance, oxygen absorption and halogen absorption and a packing material obtained from the resin compsn. SOLUTION: A hydrotalcite compd. represented by M<2+> 1-x M<3> x (OH)2 A<n-> x/n m1 H2 O [wherein M<2+> and M3+ are respectively divalent metal and trivalent metal ions, A<n-> is sulfur and phosphorus lower oxide anions selected from SO3 <2-> , H3 PO3 <2-> and H2 PO3 <-> , x and m1 are o<x<0.5 and o<=m1 ] and lighium aluminate represented by Li1-y M<2+> y M2 <3+> (OH)6 A<n-> (1+y)/n m2 H2 O [wherein M<2+> and M<3+> are same ions as methioned above, A<n-> is same as mentioned above and y and m2 are 0<=y<0.5 and o<=m2 ] are contained as effective components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel oxygen and / or
Further, the present invention relates to an antioxidant useful as a halogen scavenger and a resin composition containing the antioxidant and having excellent oxidation resistance, oxygen absorption and halogen absorption, and a packaging material and a packaging container obtained from the resin composition. . More specifically, it relates to a novel antioxidant, oxygen absorber and halogen absorber containing hydrotalcites and / or lithium aluminates containing a reducing compound as a constituent anion between layers as an active ingredient. Furthermore, by blending the antioxidant with a resin, the resin itself can be prevented from being oxidized by oxygen or halogen, and the freshness of a food or the like packaged with the resin can be maintained by absorbing oxygen. The present invention relates to a composition and a resin material.

[0002]

BACKGROUND OF THE INVENTION Plastics, especially polypropylene,
Polyolefins such as polyethylene, nylon, spandex, rubber-based polymers, petroleum products and foods, etc. are subject to undesirable changes due to oxygen and / or halogen. In order to suppress this, an antioxidant is usually added. The necessary conditions as an antioxidant are summarized as follows. 1) Excellent antioxidation performance, 2) Good compatibility with the polymer, no blooming on the surface, 3) Stable polymer processing temperature and no volatilization, 4) White polymer itself Difficult to color, 5) Insoluble in water and oil, 6) Nontoxic, 7) Inexpensive. As antioxidants used in plastics and rubber, which are the largest market for antioxidants, there are organic antioxidants made from phenol-based, sulfur-based, and phosphorus-based organic compounds as raw materials. These organic antioxidants have problems in volatility and heat resistance. In order to improve volatility and heat resistance, development of high molecular weight antioxidants has also been advanced. However, the problems of volatility and heat resistance are still insufficiently solved, and it tends to be more expensive and more toxic.

[0003]

Many of the above organic antioxidants are volatile and have problems with toxicity, and the less volatile, the more expensive they tend to be. Further, since the desired antioxidant effect cannot be sufficiently exhibited by itself, it is generally necessary to use the phenol type and the sulfur type or phosphorus type together. On the other hand, inorganic compounds such as sodium sulfite and phosphorous acid are used as antioxidants for foods. However, since it is water-soluble, it cannot be used for plastics or rubbers, although it has no problems of volatility, toxicity, and cost. The present invention overcomes the drawbacks of the above-mentioned organic antioxidant and inorganic antioxidant and is inexpensive and simultaneously satisfies all the requirements 1) to 7) that an antioxidant should have.
Further, it is an object of the present invention to provide a novel antioxidant suitable for plastics and rubbers, a resin composition containing the antioxidant, and a packaging material containing the resin composition. Furthermore, the present invention provides plastic and rubber with oxygen-absorbing property and / or halogen-absorbing property, and prevents packaging materials such as foods produced from these resins from degrading the contents such as foods due to oxygen. To aim. A further object of the present invention is to provide a halogen scavenger that traps halogen in a halogen-containing resin such as vinyl chloride or rubber. Another object of the present invention is to prevent deterioration of polyethylene water pipes, spandex swimwear, etc. due to chlorine in chlorine-sterilized tap water or pool water.

[0004]

The present invention provides the following formula (1): M 2 ⁺ _1-x M ³⁺ _x (OH) _{2 An} ^- _{x / n} · m ₁ H ₂ O (1) , M ²⁺ and M ³⁺ are divalent and trivalent metal ions, respectively, preferably M ²⁺ is Mg ²⁺ and / or Zn ²⁺ , M ³⁺ is Al ³⁺ , and A ^n- Is SO ₃ ^2- , S ₂ O
₃ ^2-, S ^2-, polysulfide _{^{ions, HPO 2 2-, H 2 PO}} 2 -,
It shows at least one of n-valent reducing anions selected from lower oxides of sulfur and phosphorus such as HPO ₃ ²⁻ and H ₂ PO ₃ ⁻ , and x and m ₁ are 0 <x <0.5 and 0, respectively. ≤ m ₁
Range. ] Or a hydrotalcite compound represented by the following formula (2) Li _1-y M ²⁺ _y M ³⁺ ₂ (OH) ₆ ^An- _{(1 + y) / n} · m ₂ H ₂ O ( 2) [wherein M ²⁺ represents a divalent metal ion, preferably Mg ²⁺ and / or Zn ²⁺ , M ³⁺ represents a trivalent metal ion, preferably Al ³⁺ , and A ^n- Has the same meaning as in formula (1),
y and m ₂ is in the range of 0 ≦ y <0.5, 0 ≦ m _2, respectively. ] An antioxidant for resins and / or rubbers, which comprises lithium aluminate represented by the formula [1] as an active ingredient. Furthermore, the present invention is characterized by containing 100 parts by weight of the resin and / or rubber and 0.001 to 20 parts by weight of the antioxidant represented by the above formula (1) and / or formula (2). A resin and / or rubber composition having excellent oxidation resistance is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted earnest research to develop a novel antioxidant that satisfies all the above-mentioned requirements necessary as an effective antioxidant for plastics and rubbers, and as a result, the following conclusions were obtained. Came to get. It is believed that the above-mentioned drawbacks of the organic antioxidants can be solved by introducing an inexpensive inorganic lower oxide such as sodium sulfite into the anion site constituting hydrotalcites or lithium aluminates. That is, a water-soluble lower oxide such as sodium sulfite is added to formula (1) or formula (2)
It was discovered that by converting it to a compound, it becomes insoluble in water and oil and can be used in resins and rubber, and the antioxidant effect inherent in lower oxides is not lost but rather strengthened. did. Further, it has been discovered that the antioxidant of the present invention is excellent in its action and effect even when it is used alone without being used in combination with a phenolic antioxidant. Hereinafter, the term "antioxidant" is used in the present invention, including applications such as halogen scavengers.

Hydrotalcites or lithium aluminates are the most stable compounds because they contain hydroxides of Mg and Al as main components. The price is relatively low, and submicron-order fine particles can be produced by selecting the synthesis conditions. In addition, since the refractive index is very close to that of resins such as polypropylene and polyethylene, it has excellent transparency. The fine particles of hydrotalcite or lithium aluminate may be surface-treated with various conventionally known surface-treating agents to improve dispersibility and compatibility with resins and rubbers.
Therefore, when adding an inorganic compound, there is a problem such as impairing transparency of resin or rubber, or appearance failure due to poor dispersion, and impairing mechanical strength such as tensile strength.
The antioxidants of the present invention are not shown.

Lower oxide anions incorporated in the structure of hydrotalcites or lithium aluminates react directly with oxygen and / or halogens to form stable higher oxide ions. Therefore, when it is added in a small amount, it acts as an antioxidant for plastics and rubbers, and when it is added in a relatively large amount, it acts as an absorber for oxygen and / or halogens that enter the plastics and rubbers. When it acts as an oxygen absorber, it can be used as a freshness-retaining agent by preventing oxidation of liquor, foods, fish, flowers, etc., and can also be used as an ingredient to be incorporated into plastic or rubber packaging materials. Further in these fields of application, the antimicrobial agent previously invented by the present inventor; namely a solid solution of a hydroxide or oxide of Mg and / or Ca and a hydroxide or oxide of Zn and / or Cu ( JP-A-6-7
2816, JP-A-6-65011 and Japanese Patent Application No. 6-79714), and the antioxidant of the present invention can be used together to further enhance the freshness-retaining function.

In the compounds of formula (1) and formula (2) of the present invention, at least the compounds of the present invention excluding A ^n- are known as hydrotalcites and lithium aluminates, both in terms of substance and production method. [For example, F. Cavan
i., T.Trifiro, A.Vaccari, Catalysis Today, 11,173 (1
991), MJHernandez-Moreno, MAUlibarri, JLRend
on and CJSerna, Phys. Chem. Minerals 12,34 (198
Five)]. Next, a method for producing the compounds of formula (1) and formula (2) of the present invention will be described. In the compound of the formula (1), a lower oxide anion for the purpose of a water-soluble metal salt such as Mg, Al and Li as a raw material
By reacting the compound of the formula (2) with a pH of about 8 or more, a pH of about 11 or more, or NO ₃ ⁻ , Cl ⁻ , Br ⁻ , C.
It can be produced by subjecting the compound of formula (1) or formula (2) having H ₃ COO ⁻ or the like as a constituent anion to the target lower oxide anion. Preferably, the compound produced by the above method is treated at about 110 ° C to about 200 ° C.
It is recommended that hydrothermal treatment be performed for about 5 hours or longer. The compound of formula (2) can also be produced by a method of hydrothermally treating aluminum hydroxide and a lithium compound such as lithium carbonate at about 100 to about 180 ° C.

When added to resins and rubbers, in order to satisfy good dispersibility, appearance of molded articles, good antioxidant ability, whiteness, etc., the average secondary particle diameter is at least 5 μm.
Hereafter, it is necessary that the thickness is preferably 1 μm or less.
Also in the compound of formula (1), the Mg ²⁺ and / or Zn ²⁺ as M ^2+, it is preferable to use Al ³⁺ as M ^3+. Also in the compound of formula (2), the Mg ²⁺ and / or Zn ²⁺ as M ^2+, it is preferable to use Al ³⁺ as M ^3+. It is particularly preferable to use S ₂ O ₃ ²⁻ as the lower oxide anion A ⁿ⁻ for both the compounds of formula (1) and formula (2).

In order to improve the dispersibility of the compounds of the formulas (1) and (2) in resins and rubbers, it is preferable to use them by surface treatment with the following known surface treatment agents. Specific examples of the surface treatment agent are shown below. Higher fatty acids such as stearic acid, palmitic acid, lauric acid and oleic acid; alkali metal salts of the above higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl alcohol; amide bond sulfate ester salts, ester bond sulfate esters Salt, ester linked sulfonate,
Amide bond sulfonate, ether bond sulfonate,
Anionic surfactants such as ether-bonded alkylallyl sulfonates, ester-bonded alkylallyl sulfonates and amide-bonded alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc. or a mixture of both. And phosphoric acid esters of their acid form or alkali metal salts or amine salts; vinylethoxysilane, vinyltris (2-methoxy-ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane. , Β (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and other silane coupling agents; isopropyltriisostea Titanate coupling agents such as royl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tridecylbenzenesulfonyl titanate; aluminum coupling agents such as acetoalkoxy-aluminum diisopropylate; glycerin monostearate;
Esters of polyhydric alcohols such as glycerin monooleate and fatty acids.

Formulas (1) and (2) depending on the surface treatment agent
The coating treatment of the compound (1) can be carried out by a wet method or a dry method known per se. For example, as a wet method, the surface treatment agent may be added to the slurry of the compound of formula (1) or formula (2) in a liquid or emulsion form and mechanically stirred to sufficiently mix them. As the dry method, the powder of the compound of formula (1) or formula (2) is added to the surface treatment agent in a liquid, emulsion or solid state with sufficient stirring by a mixer such as a Henschel mixer, and the mixture is heated or not heated. It should be mixed well. The amount of the surface treatment agent added can be appropriately selected, but it is preferably about 0.1 to about 10% by weight based on the weight of the compound of the formula (1) or formula (2).

Examples of resins and rubbers used in the antioxidant-containing resin or rubber composition of the present invention are as follows. Polyethylene, copolymers of ethylene and other olefins, ethylene and vinyl acetate, ethyl acrylate,
Or a copolymer with methyl acrylate, polypropylene, a copolymer of propylene and other α-olefin, polybutene-1, polystyrene, a copolymer of styrene and acrylonitrile, a copolymer of ethylene and propylene diene rubber or butadiene, and acrylonitrile. Copolymer (ABS) of butadiene and styrene, polymethylpentene, vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene, chlorinated polypropylene, polyamide, polyimide, polyethylene terephthalate,
Thermoplastic resin such as polybutylene terephthalate, polysulfone, polyvinyl alcohol, etc., epoxy resin, xylene resin, phenol resin, thermosetting resin such as polyurethane, SBR, BR, TR, EPDM, EPM, NB
Rubbers such as R, CR, IIR, urethane rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, ethylene / acrylic rubber, natural rubber. Among the above resins, polyethylene, polypropylene, polystyrene, ABS and polyvinyl chloride resins are usually particularly preferably used.

The antioxidant of the present invention is spandex,
Synthetic fibers such as polypropylene fiber, polyester fiber, acrylic fiber, etc., blending with petroleum products such as gasoline, kerosene, light oil lubricating oil, or packaging materials for food such as lard, butter, soybean oil, meat, fruits, vegetables or in foods. It can also be used by being contained in. The mixing amount of the antioxidant of the present invention with respect to the resin and the rubber is 1
It is about 0.001 to about 50 parts by weight, preferably about 0.01 to about 10 parts by weight, relative to 00 parts by weight. The oxidation resistant resin and / or rubber composition of the present invention may contain other conventional additives in addition to the antioxidant of the present invention. Examples of such additives include the following. Phenol type antioxidant, phosphorus type or sulfur type antioxidant, ultraviolet absorber, heat stabilizer, antistatic agent, pigment, foaming agent, plasticizer, lubricant, acid and halogen neutralizing agent, vulcanizing agent, crosslinking agent etc.

The present invention will be described in more detail based on the following examples.

【Example】

Example 1 Commercially available hydrotalcites (chemical composition: Mg _4.5 Al ₂
(OH) ₁₃ CO ₃ · 3.5H ₂ O, BET specific surface area 12 m
² / g, average secondary particle size 0.42 μm, Kyowa Chemical Industry Co., Ltd., “DHT-4”) 100 g was suspended in about 2 liters of water, and 0.4 N HNO ₃ 1 liter was stirred to about pH.
4, added while keeping the temperature at 25 ° C., and converted into NO ₃ type hydrotalcite. Then 0.2 mol / l Na
Add 2 liters of ₂ S ₂ O ₃ and continue stirring for about 20 minutes,
NO ₃ ^{− of} hydrotalcite was ion-exchanged with S ₂ O ₃ ²⁻ . After filtration, hydrotalcite was mixed with a stirrer to about 4
After emulsifying and dispersing in water at 0 ° C., a sodium laurate aqueous solution (containing 3 g of sodium laurate) melted in 100 g of warm water was added with stirring to perform surface treatment. Subsequently, it was filtered, washed with water, and then vacuum dried at about 60 ° C. Similarly, a sample before surface treatment was prepared, and a chemical analysis of this was performed. The chemical composition was as follows. Mg _4.5 Al ₂ (OH) ₁₃ (S ₂ O ₃ ) _0.9 (CO ₃ ) _0.1
mH ₂ O The X-ray diffraction pattern of this product was the same as that of hydrotalcite, although it was shifted to a lower angle. As a result of thermal analysis of this sample in air, there was a strong exothermic peak due to oxygen absorption at about 210 ° C., and weight increase due to oxygen absorption was observed around this temperature (FIG. 1). On the other hand, for example, Na ₂ S ₂ O ₃ .5H ₂ O decomposed at about 135 ° C., and substantially no heat generation due to oxygen absorption was observed (FIG. 2).

After uniformly mixing 100 parts by weight of polypropylene polymerized with a Ziegler-Natta catalyst with 0.05 part by weight of calcium stearate and 0.10 part by weight of the above surface-treated S ₂ O ₃ type hydrotalcite, It was melt-kneaded at 240 ° C. using an extruder, cooled with water, and dried. This kneading was repeated up to 5 times. Melt flow index (hereinafter also referred to as MI) and yellowing degree were evaluated for each sample obtained by repeating kneading once, three times and five times. For the yellowing degree, the b value was measured using a Hunter color difference meter. Table 1 shows the results. In polypropylene, the main chain is broken due to deterioration during processing, the melt viscosity is reduced, and the MI is increased. Therefore, the smaller the increase in MI, the more suppressed the oxidation. That is, the value of MI indicates the quality of processing stability. Further, the less the degree of yellowing, that is, the less coloring, the higher the commercial value, and this yellowing is also caused by oxidation.

Example 2 0.10 part by weight of the surface-treated S ₂ O ₃ type hydrotalcite obtained in Example 1, 0.10 part by weight of phenolic antioxidant Irganox 1010 and steer In the same manner as in Example 1, 0.05 part by weight of calcium phosphate was melt-kneaded with 100 parts by weight of polypropylene.
The MI and yellowing degree of each of the obtained samples were evaluated. Table 1 shows the results. The oxidation resistance of the antioxidant of the present invention was further improved by using it in combination with a phenolic antioxidant.

Example 3 100 g of NO ₃ type hydrotalcite obtained in the same manner as in Example 1 was emulsified in 1.5 liter of deionized water, and then Na ₂ S ₂ O ₃ was stirred. · 7H ₂ O was added 94 g, it was allowed to react for approximately 30 minutes. Then, it was filtered, washed with water, and further washed with about 1 liter of acetone. The obtained cake was put into a dryer and dried at about 60 ° C. The chemical composition of the dried product was as follows. Mg _4.5 Al ₂ (OH) ₁₃ (SO ₃ ) _0.92 (CO ₃ ) _0.08
mH ₂ O The X-ray diffraction pattern of this product was the same as that of hydrotalcite, although it was slightly shifted to a lower angle. As a result of thermal analysis of this sample in air, there was a strong exothermic peak due to oxygen absorption at about 197 ° C., and a slight weight increase due to oxygen absorption was observed around this temperature (FIG. 3). The calorific value was about 55 μV / 10.4 mg. On the other hand, SO
Thermal analysis of Na ₂ SO ₃ under the same conditions as for type ₃ hydrotalcite revealed that an extremely weak exothermic peak of about 6 μV / 10.7 mg was only observed at about 295 ° C. (FIG. 4).

The obtained SO ₃ type hydrotalcite was used as a linear low density polyethylene (hereinafter also referred to as LLDPE) 10
0.05 parts by weight and 0,05 parts by weight of calcium stearate were uniformly mixed and then kneaded at 220 ° C. for a maximum of 5 times in total to obtain a sample. The MI and yellowing degree of each of the obtained samples were evaluated.
Table 1 shows the evaluation results. Polyethylene causes cross-linking due to deterioration during processing, melt viscosity increases, and MI decreases.

Example 4 BET specific surface area 9 m ² / g, average secondary particle diameter 0.60 μ
78 g of aluminum hydroxide of m was placed in 800 ml of deionized water and emulsified using a stirrer. Then, 2.8 g of Li ₂ CO ₃ was added to and dissolved in this, and hydrothermal treatment was carried out at 140 ° C. for 10 hours using an autoclave. The hydrothermally treated product was filtered, washed with water, emulsified in 1 liter of water, and 0.7 liter of a 0.5 mol / liter H ₃ PO ₂ aqueous solution was added with stirring while maintaining the pH at about 3. After that, it was filtered, washed with water, and vacuum dried at about 70 ° C. The results of chemical analysis of the dried product were as follows. _{LiAl 2 (OH) 6 (HPO} 2) 2- 0.5 · mH 2 O X -ray diffraction pattern of this compound LiAl ₂ (OH) ₆ (C
O ₃₎ ^2- _0.5 · mH was ₂ O and substantially the same. To 100 parts by weight of LLDPE used in Example 3, 0.05 parts by weight of this HPO ₂ type lithium aluminate and 0.05 parts by weight of calcium stearate were mixed, and the same procedure as in Example 3 was performed to obtain a sample. . Table 1 shows the evaluation results of MI and yellowing degree of each sample.

Comparative Example 1 A polypropylene sample was obtained in the same manner as in Example 1 except that the antioxidant was not added. Each sample was evaluated for MI and degree of yellowing. Table 1 shows the evaluation results.

Comparative Example 2 A sample of LLDPE was obtained in the same manner as in Example 3, except that the antioxidant was not added. Each sample was evaluated for MI and degree of yellowing. Table 1 shows the evaluation results.

Example 5 To 500 ml of water containing 100 ppm of chlorine, 1 g of the unsurface-treated S ₂ O ₃ type hydrotalcite obtained in Example 1 was added, and the mixture was stirred for about 30 minutes. It was measured by absorption spectrometry. The chlorine concentration in water is 1.
It was 0 ppm.

Table 1 Example 1 Example 2 Comparative Example 1 Number of extrusions MI b MI b MI b 1 3.2 2.9 2.6 2.1 8.7 3.8 3 4.1 4.9 3.2 3.7 14.0 10.3 5 5.6 8.0 4.3 6.9 21.1 16.8 Note: The unit of MI is g / 10 minutes.

Table 1 (continued) Example 3 Example 4 Comparative Example 2 Number of extrusions MI b MI b MI b 1 1.8 -4.5 1.7 -3.5 1.5 7.2 3 1.7 -2.4 1.6 -2.4 1.2 7.5 5 1.6 1.3 1.5 -1.7 1.0 7.8

[0025]

EFFECTS OF THE INVENTION According to the present invention, there is provided an antioxidant which is excellent in oxidation resistance, oxygen absorptivity and halogen absorptivity and which solves the drawbacks of conventional organic antioxidants and inorganic antioxidants. Provided. That is, according to the present invention, there is provided an antioxidant which is neither volatile nor toxic, has excellent heat resistance, and can be manufactured at low cost. Further, according to the present invention, since the refractive index is close to that of resin or rubber, an antioxidant is provided which is excellent in transparency when compounded in resin or rubber, and which is excellent in dispersion and compatibility with resin or rubber. . Further according to the invention,
Provided are a resin composition containing the antioxidant of the present invention, which prevents deterioration of resins and rubbers due to oxygen and halogen, and a resin material made of the resin composition, which is excellent in freshness-keeping performance of contents such as foods. .

[Brief description of drawings]

FIG. 1 is a graph showing the thermal analysis results of S ₂ O ₃ type hydrotalcite obtained in Example 1.

FIG. 2 is a graph showing the results of thermal analysis of Na ₂ S ₂ O ₃ .5H ₂ O.

FIG. 3 is a graph showing a thermal analysis result of SO ₃ type hydrotalcite obtained in Example 3.

FIG. 4 is a graph showing the results of thermal analysis of Na ₂ SO ₃ .

Claims (7)

[Claims] 1. The following formula (1) M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ^n- _{x / n} · m ₁ H ₂ O (1) [wherein M ²⁺ and M ³⁺ Are divalent metal and trivalent metal ions, respectively, and A ^n- is SO ₃ ²⁻ , S ₂ O ₃ ²⁻ , S ²⁻ ,
Polysulfide _{^{ions, HPO 2 2-, H 2 PO}} 2 -, HPO 3 2-,
It represents at least one anion of a lower oxide of sulfur and phosphorus selected from H ₂ PO ₃ ^— , and x and m ₁ are in the range of 0 <x <0.5 and 0 ≦ m ₁ , respectively. ] Or a hydrotalcite compound represented by the following formula (2) Li _1-y M ²⁺ _y M ³⁺ ₂ (OH) ₆ ^An- _{(1 + y) / n} · m ₂ H ₂ O ( 2) [In the formula, M ²⁺ and M ³⁺ represent a divalent metal and a trivalent metal ion, respectively, and A ⁿ⁻ has the same meaning as in the formula (1),
y and m ₂ is in the range of 0 ≦ y <0.5, 0 ≦ m _2, respectively. ] The antioxidant containing lithium aluminate represented by these as an active ingredient. 2. The formula (1) and the formula (2) according to claim 1.
In, M ²⁺ is Mg ²⁺ and / or Zn ²⁺ ,
M ³⁺ is Al ³⁺ and A ⁿ⁻ is SO ₃ ²⁻ and / or S ₂
An antioxidant, which is O ₃ ²⁻ . 3. The formula (1) and the formula (2) according to claim 1.
Is selected from the group consisting of higher fatty acids, anionic surfactants, phosphoric acid esters, silane coupling agents, titanate coupling agents, aluminum coupling agents and esters of polyhydric alcohols and fatty acids. An antioxidant, which is surface-treated with at least one surface treatment agent. 4. A resin containing 100 parts by weight of the resin and 0.001 to 20 parts by weight of the antioxidant represented by the formula (1) and / or the formula (2) according to claim 1. Composition. 5. The resin composition according to claim 4, further containing 0.001 to 10 parts by weight of a phenolic antioxidant. 6. A packaging material containing the resin composition according to claim 4. 7. A halogen scavenger containing the hydrotalcite compound according to claim 1 and / or lithium aluminate as an active ingredient.