JP6164900B2 - Sulfur-based gas adsorption resin composition - Google Patents

Description

  The present invention relates to a sulfur-based gas adsorption resin composition containing an adsorbent that adsorbs a sulfur-based gas, and a molded body thereof.

  Sulfur-based gases such as hydrogen sulfide and mercaptans are harmful gases having flammability and toxicity, and cause irritating odors even in trace amounts. Furthermore, since these have high corrosivity, problems, such as corrosion, may arise in the apparatus etc. which generate | occur | produce these. Therefore, as one solution, an adsorbent for removing sulfur-based gas can be used.

  For example, in an all-solid-state lithium battery using a sulfide-based solid electrolyte membrane, there is a problem that hydrogen sulfide is generated inside when the sulfide-based solid electrolyte membrane is in contact with moisture, and the performance is significantly deteriorated. For this reason, in order to adsorb sulfur-based gas such as hydrogen sulfide in this device, for example, Patent Document 1 discloses a fluid sealant containing unvulcanized rubber as a hydrogen sulfide absorbent. However, since the ability of the unvulcanized rubber to adsorb hydrogen sulfide is not high at the use temperature of such a lithium battery, the effect of the invention described in Patent Document 1 is considered to be limited.

  On the other hand, when the adsorbent is used, the adsorbent is usually granular or powdery alone, so that the adsorbent is often used together with highly breathable fibers. However, depending on the application of the adsorbent, there are cases where it is inappropriate to use it in fibers and the like, and there is known a method in which a granular or powdery adsorbent is mixed with a resin. For example, Patent Document 2 discloses a laminated film in which a reinforcing film is laminated on a hygroscopic layer obtained by kneading a hygroscopic agent such as zeolite in LDPE. Further, Patent Document 3 discloses a sealing composition for multilayer glass and for the end portion of a solar cell panel obtained by kneading a moisture absorbent such as calcium carbonate, butyl rubber and polyolefin.

  While the resin composition containing such an adsorbent can be processed into a molded body and used in various modes for various applications, the adsorbent is used alone or in combination with highly breathable fibers. It is known that the capacity of the adsorbent may be reduced as compared with the case where it is used.

JP 2009-2181010 A JP-A-2005-280188 JP 2011-231309 A

  Then, an object of this invention is to provide the resin composition with the high adsorption capability of sulfur type gas which can be used for various uses, and its molded object.

The present inventors have found that the above problems can be solved by the following means.
[1] A sulfur-containing binder comprising an aromatic vinyl-diene copolymer having a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a diene monomer, and an inorganic adsorbent that chemically adsorbs hydrogen sulfide. Resin composition for gas adsorption.
[2] The aromatic vinyl monomer is selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene and mixtures thereof. [1] The resin composition described in 1.
[3] The resin according to [1] or [2], wherein the diene monomer is selected from linear or branched aliphatic diene or alicyclic diene having 4 to 10 carbon atoms and a mixture thereof. Composition.
[4] The resin composition according to [3], wherein the diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, and a mixture thereof.
[5] The resin composition according to [1], wherein the copolymer is a styrene-butadiene copolymer.
[6] Any of [1] to [5], wherein the inorganic adsorbent includes a compound containing at least one metal selected from copper, iron, zinc, manganese, cobalt, nickel, zirconium, and a lanthanoid element. The resin composition according to one item.
[7] The resin composition according to [6], wherein the inorganic adsorbent is copper (II) silicate.
[8] The resin composition according to any one of [1] to [7], wherein the binder further includes a thermoplastic resin other than the aromatic vinyl-diene copolymer.
[9] The resin composition according to [8], wherein the thermoplastic resin is a polyolefin resin.
[10] The resin composition according to [8] or [9], wherein the aromatic vinyl-diene copolymer is 20% by weight or more based on the weight of the binder.
[11] A molded article of the resin composition according to [1] to [10].

  The resin composition for adsorbing sulfur-based gas according to the present invention exhibits a high adsorption capacity for sulfur-based gas and can be molded into various modes. Since sulfur-based gas is adsorbed without affecting the temperature and humidity of the gas, it can be used in various applications. For example, when the resin composition of the present invention is molded and used in an all-solid-state lithium battery using a sulfide-based solid electrolyte membrane, the molded body adsorbs hydrogen sulfide generated inside, The battery performance can be maintained for a long time.

<Sulfur-based gas adsorption resin composition of the present invention>
The resin composition of the present invention includes a binder containing an aromatic vinyl-diene copolymer having a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a diene monomer, and an inorganic adsorbent that chemically adsorbs hydrogen sulfide. including. Usually, when the adsorbent is dispersed in the resin, the performance of the adsorbent is greatly reduced due to the low gas permeability of the resin. However, the present inventors have discovered that the resin composition having the constitution of the present invention can unexpectedly maintain a certain level of performance with respect to the adsorption capacity of the sulfur-based gas. Although not bound by theory, it is presumed that this is due to the high permeability of the sulfur-based gas to the aromatic vinyl-diene copolymer. Here, the sulfur-based gas refers to hydrogen sulfide and thiols such as methanethiol and ethanethiol.

(binder)
The binder used in the resin composition of the present invention includes an aromatic vinyl-diene copolymer having a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a diene monomer. The aromatic vinyl-diene copolymer is preferably contained in an amount of 10% by weight, 20% by weight, 30% by weight, 40% by weight or more, 50% by weight or more, or 70% by weight or more based on the total weight of the binder. The binder may be composed entirely of an aromatic vinyl-diene copolymer.

  The aromatic vinyl-diene copolymer may contain other repeating units in addition to the repeating unit derived from the aromatic vinyl monomer and the repeating unit derived from the diene monomer. This aromatic vinyl-diene copolymer can be prepared by ionic polymerization or radical polymerization, and can also be prepared by solution polymerization or emulsion polymerization. The proportion of the repeating unit derived from the aromatic vinyl monomer in the copolymer is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less. It is. The proportion of the repeating unit derived from the diene monomer in the copolymer is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less. .

  Examples of the aromatic vinyl monomer used to obtain this copolymer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, and the like. Can be used alone or in combination of two or more.

  Further, examples of the diene monomer include linear or branched aliphatic diene or alicyclic diene having 4 to 10 carbon atoms and mixtures thereof. Specifically, 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1 , 5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3 butadiene, 2-ethyl-1,3 butadiene, 1,2-heptadiene, 1,3-heptadiene, 1 , 4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene, 3,5-heptadiene, cyclopentadiene, dicyclopentadiene, etc. These can be used alone or in combination of two or more. Among these, 1,3-butadiene, isoprene, and 1,3-pentadiene are preferable.

  Examples of such copolymers include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene copolymer (SIR), styrene-isoprene styrene block. Copolymer (SIS), α-methylstyrene-butadiene copolymer (MSBR), vinylpyridine-styrene-butadiene copolymer (PSBR), carboxylated SBR (XSBR) copolymerized with acrylic acid, acrylonitrile- A butadiene-styrene copolymer (ABS) or a derivative thereof such as a hydrogenated styrene butadiene copolymer may be mentioned. These may be cross-linked, but in view of moldability, they are preferably in an uncrosslinked state.

The weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer is preferably 2,000 or more, 5,000 or more, 10,000 or more, or 100,000 or more, 2,000,000 or less, It is preferable that it is 1,500,000 or less, 1,200,000 or less, 1,000,000 or less, or 800,000 or less. The ratio Mw / Mn between the copolymer Mw and the number average molecular weight (hereinafter referred to as “Mn”) is preferably 1.0 or more, and is 10.0 or less, 7.0 or less, 5.0 or less. Or 2.5 or less. Mw and Mn are values measured by gel permeation chromatography (GPC) using polystyrene as a standard sample. The toluene solution viscosity at 25 ° C. is 100 mPa · s or more, 500 mPa · s or more, or 1, when the viscosity of the toluene solution containing 25% by weight of this copolymer is measured using a Canon Fenske type kinematic viscometer. 000 mPa · s or more, preferably 100,000 mPa · s or less, 50,000 mPa · s or less, or 30,000 mPa · s or less. The Mooney viscosity ML _{(1 + 4)} measured according to JIS K6300 is preferably 30 or more, 40 or more, 45 or more, or 50 or more, and preferably 80 or less, 70 or less, or 60 or less. .

  In addition to the aromatic vinyl-diene copolymer, other thermoplastic resins can be blended in the binder. By using a thermoplastic resin in combination with the above-mentioned aromatic vinyl-diene copolymer, the degree of freedom in designing the physical properties of the resin composition of the present invention, such as heat resistance, workability, and sealing properties, is increased. Can do. For example, when the binder consists only of the above aromatic vinyl-diene copolymer, the softening temperature of the resin composition of the present invention may be about 50 ° C. to 80 ° C., but this softening temperature is not acceptable. It may be enough. Therefore, by blending another thermoplastic resin with the binder, it is possible to improve the softening temperature, preferably 5 ° C. or higher, 10 ° C. or higher, or 30 ° C. or higher, while maintaining a certain level of sulfur gas adsorption capacity. . Here, the softening temperature is a temperature at which the slope of the storage elastic modulus measured while increasing the temperature at 3 ° C./min by DMA Q-800 manufactured by TA Instruments, a dynamic viscoelasticity measuring apparatus, starts to change.

  The amount of the thermoplastic resin to be blended is an amount such that the thermoplastic resin is 10% by weight, preferably 20% by weight or more based on the weight of the binder in order to obtain the effect of the blending. On the other hand, in order to obtain the effect of the present invention, the amount of the polyolefin resin added is 90% by weight or less, preferably 80% by weight or less.

  Examples of the thermoplastic resin that can be blended include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin polyarylate, and liquid crystalline polyester; polystyrene resin, high-impact polystyrene resin (HIPS) Styrene resins such as acrylonitrile-styrene copolymer (AS), acrylonitrile-styrene-acrylic rubber copolymer (ASA), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES); polyethylene resin, polypropylene resin, Polyolefin resins such as cyclic olefin resins and cyclic olefin copolymer resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; ; Polyphenylene sulfide resins; polysulfone resins; polycarbonate resins; polyoxymethylene resins, polymethacrylate resins, polyvinyl chloride resins, polytetrafluoroethylene resins, various elastomers, and the like.

  Examples of the polyolefin-based resin include polyethylene (for example, low-density polyethylene such as linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc.), polypropylene, and ethylene-propylene copolymer. Examples of the polyolefin include a copolymer of ethylene or propylene and another α-olefin, and a copolymer of ethylene and an oxygen-containing ethylenically unsaturated monomer. Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and the like. Examples of the oxygen-containing ethylenically unsaturated monomer include vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and vinyl alcohol. Moreover, when polyolefin is a copolymer, a random copolymer, a block copolymer, etc. are mentioned, for example.

  As the thermal characteristics of the thermoplastic resin that can be used, for example, when the melt mass flow rate is measured in accordance with JIS K6922-1 using polyethylene conditions, preferably 0.1 g / 10 min or more, 0 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 200 g / 10 min or less, 100 g / 10 min or less, 50 g / 10 min or less, or 30 g / 10 min or less. . In addition, for example, the melt mass flow rate is preferably 0.1 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 3.0 or more when measured according to JIS K7210 using polypropylene conditions. It is 10 min or more, 5.0 g / 10 min or more, or 10 g / 10 min or more, and is 200 g / 10 min or less, 100 g / 10 min or less, 50 g / 10 min or less, or 30 g / 10 min or less.

(Sulfur-based gas adsorbent)
The sulfur-based gas adsorbent used in the present invention is an inorganic adsorbent that chemically adsorbs hydrogen sulfide. That is, the sulfur-based gas adsorbent used in the present invention is an inorganic adsorbent having an adsorption mechanism such as adsorbing by reacting with hydrogen sulfide on its surface to form a sulfide or adsorbing hydrogen sulfide by a coordinate bond. It is. This inorganic adsorbent is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more with respect to 100 parts by weight of the resin contained in the composition of the present invention in consideration of kneadability and adsorption performance Preferably, it is contained in an amount of 500 parts by weight or less, 300 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, or 30 parts by weight or less.

  Examples of such inorganic adsorbents include compounds containing at least one metal selected from copper, iron, zinc, manganese, cobalt, nickel, zirconium, and lanthanoid elements. As the compounds of zirconium and lanthanoid elements, mention may be made in particular of these hydroxides or hydrated oxides, for example, adsorbents described in JP-A-1-223968. Examples of the zinc and manganese compounds include tetravalent metal phosphates on which these metal ions are supported, and examples include adsorbents described in JP-A-10-155883.

A particularly preferable inorganic adsorbent is a metal silicate containing at least one metal selected from copper, zinc, manganese, cobalt, and nickel. More preferably, the elemental composition (mole) ratio of metal to silicon is a metal. /Silicon=0.60 to 0.80. Such an inorganic adsorbent can be produced by reacting a metal salt with an alkali silicate salt. As the metal salt, an inorganic salt such as sulfuric acid, hydrochloric acid or nitric acid and / or an organic salt such as formic acid, acetic acid or oxalic acid of at least one metal selected from copper, zinc, manganese, cobalt and nickel is used. be able to. Among these, copper (I), copper (II), and zinc (I) are preferable as the metal. Examples of the silicate include M ₂ O.I. nSiO ₂ . Mention may be made of alkali silicate salts of the formula xH ₂ O (wherein M represents a monovalent alkali metal, n is 1 or more, and x is 0 or more). The most preferred metal silicate is copper (II) silicate which is a reaction product of copper (II) sulfate and sodium silicate, and is described in, for example, JP-A-2011-104274. Moreover, in a commercial item, Kesmon (trademark) NS-10C, NS-10N, NS-20C, etc. of Toagosei Co., Ltd. are mentioned.

  The adsorption capacity of the sulfur-based gas of the adsorbent used in the present invention is preferably 10 ml / g or more, 20 ml / g or more, or 40 ml / g or more of methyl mercaptan per 1 g of adsorbent at 25 ° C. and / or sulfurized. It is 20 ml / g or more, 40 ml / g or more, or 60 ml / g or more with respect to hydrogen.

When the adsorbent used in the present invention is in a powder form, the preferred particle size d50 is preferably 0.5 to 10.0 μm, more preferably 1.0 to 8.0 μm, and more preferably 2 0.0-5.0 μm. The d90 particle size is preferably 1 to 50 μm, more preferably 2 to 30 μm. The closer the d50 and d90 values are, the closer the particle size of the adsorbent becomes, and the better the workability and the like. Therefore, the d90 value is preferably between 2 and 15 times d50, more preferably 3 Between 12 and 12 times. In this case, d50 and d90 are measured by a laser diffraction method, specifically, by a laser diffraction particle size distribution measuring device “MS2000” manufactured by Malvern. Also preferred specific surface area, ^{50 m} 2 / g or more, 100 m ² / g or more, 200 meters ² / g or more, or at 250 meters ² / g or more, in this case, in compliance with ^{JIS Z8830 -2001,} manufactured by Horiba, Ltd. continuous It measures using a flow type surface area meter "SA-6200".

  The above adsorbents can also be used in combination with other adsorbents such as activated carbon, zeolite, silica gel, aluminum silicate, hydrous zirconium oxide, zirconium phosphate, zinc oxide, and sepiolite.

(Method for producing resin composition for sulfur-based gas adsorption)
The resin composition for adsorbing sulfur-based gas of the present invention can be produced by kneading the above copolymer and adsorbent, and optionally polyolefin. For the kneading, for example, a batch kneader such as a kneader, a Banbury mixer, a mixing roll, or a continuous kneader such as a biaxial kneader is used.

(Usage method of the resin composition for sulfur gas adsorption)
The sulfur-based gas adsorption resin composition of the present invention can be used by being put in another container after production, and can be used as a molded article after being molded. Or the composition of this invention can be used with another base material, for example, can be used by impregnating a fiber. These can be given to the place where the sulfur-based gas is present or generated and the resin composition for adsorbing sulfur-based gas of the present invention or the molded product thereof can be used.

<Sulfur-Based Gas Adsorbing Molded Body of the Present Invention>
The above sulfur-based gas adsorption resin composition can be molded into various shapes such as a film, a sheet, a sphere, a column, a rectangular parallelepiped, a ring, and a cylinder. For example, the sulfur-based gas adsorption resin composition can be formed into a film or sheet by press molding, inflation method, T-die method, extrusion molding such as coextrusion or injection molding, etc. Particularly in this case, the inflation method and the T-die method are preferable.

  The molded body of the present invention can be used for, for example, a lithium battery. Such a lithium battery includes a positive electrode, a negative electrode, an electrolyte, and the above sulfur-based gas adsorption molded body in at least a container, and any element includes sulfide. For example, the positive electrode may be a metal sulfide, and / or the electrolyte may be a sulfide-based solid electrolyte membrane. As such a battery, the battery of Unexamined-Japanese-Patent No. 2012-094446 and Unexamined-Japanese-Patent No. 2012-190553 is mentioned, for example. Here, for example, a film-like molded body can be used by being bonded to any location inside an all solid-state lithium battery using a sulfide-based solid electrolyte membrane.

  Moreover, the molded object of this invention can be used like the film for food packaging as described in Unexamined-Japanese-Patent No. 62-64737 besides a lithium battery. For example, in conventional retort pouches, when raw fish and shellfish are sterilized by heating, hydrogen sulfide is generated, and this hydrogen sulfide loses the flavor peculiar to the content food, and the odor of hydrogen sulfide remains, which significantly reduces the commercial value. I will let you. In such a case, since the generated hydrogen sulfide can be adsorbed by encapsulating the resin composition of the present invention in one layer of the film constituting the retort pouch or inside, the flavor of the contents Will not be damaged.

Example 1: Evaluation of hydrogen sulfide adsorption performance of resin compositions using various polymers 100 parts by weight of the resin listed in Table 1 below, and Kesmon NS-20C (manufactured by Toagosei Co., Ltd.) 11 as a sulfur-based gas adsorbent 0.1 part by weight (phr) was kneaded with a Banbury mixer at a rotation speed of 50 rpm and a temperature of 140 ° C. for 10 minutes to obtain a kneaded body containing an adsorbent. The kneaded body was pressed with a press at a temperature of 140 ° C. and a pressure of 20 MPa for 30 seconds to obtain a 50 μm-thick sulfur-based gas adsorption sheet. However, in Comparative Example 5, no adsorbent was contained.

  This sheet is cut into 25 mm × 10 mm, put into an aluminum pack, a certain amount of 100 ppm hydrogen sulfide standard gas (remainder: nitrogen) is injected, and the amount of hydrogen sulfide in the aluminum pack after 24 hours is measured by gas chromatography (FPD). The amount of adsorption was obtained by measuring the amount of hydrogen sulfide in the aluminum pack.

  Note that asaprene 411, 432, and 437 are solution-polymerized SBR with a styrene ratio of 30%, and among these three, asaprene 411 is the highest, then asaprene 432, and the lowest is asaprene 437. . Nipol 1502 is an emulsion polymerization SBR having a styrene ratio of 23.5%.

  In Examples 1 to 4 of the present invention in which an adsorbent is contained in styrene-butadiene rubber (SBR), the amount of hydrogen sulfide adsorbed by the above measuring method is a high value of 10.0 μL / mg · 24 h or more. However, in Comparative Examples 1 to 4 containing an adsorbent in butadiene rubber (BR), polyethylene (PE), polystyrene (PS), and polypolypropylene (PP), the hydrogen sulfide adsorption amount is very low. In Comparative Example 5 containing no adsorbent, hydrogen sulfide was not adsorbed.

  In general, BR has higher gas permeability of hydrogen, nitrogen, oxygen and carbon dioxide than SBR ("Basics of New Rubber Technology", revised on January 30, 2002, Japan Rubber Association, (Refer to page 115, Table 5.14). Normally, it is natural to think that hydrogen sulfide also has lower transmittance than SBR. Therefore, in a resin composition in which an adsorbent is contained in SBR and BR in the same manner, it is normal that the BR composition can exhibit higher adsorption performance than the SBR composition. However, in the above experiment, a result opposite to this estimation was obtained, and the SBR composition showed unexpectedly high adsorption performance. Without being bound by theory, it is presumed that BR has a higher transmittance for hydrogen, nitrogen, oxygen, and carbon dioxide, but SBR has a higher transmittance for hydrogen sulfide.

Example 2: Evaluation of hydrogen sulfide adsorption performance and thermal characteristics of the resin composition of the present invention blended with polyolefin resin Next, 11.1 phr of adsorbent (Kesmon NS-20C (Toagosei)) was added to PE (Petrocene 342 ( Tosoh Corporation)) or PP (Novatech FL02A (Nippon Polypro Corporation) and SBR (Asaprene 432 (Asahi Kasei Chemicals Corporation)) were kneaded with a Banbury mixer at a rotation speed of 50 rpm and a constant temperature for 10 minutes. The same method was used to form a sheet, and the adsorption performance was further evaluated in the same manner as in Example 1. Further, their softening temperature was examined with DMA Q-800 manufactured by TA Instruments.

  From this result, when PE is blended with SBR, the softening temperature can be increased to a certain degree while increasing the amount of hydrogen sulfide adsorbed, and when PP is blended, the softening temperature is maintained while maintaining a certain amount of adsorption. It can be seen that can be greatly increased. Therefore, it has been found that blending a polyolefin resin with the composition of the present invention is particularly useful in designing the thermal characteristics of the composition.

  The resin composition for adsorbing sulfur-based gas of the present invention is useful because it exhibits a high adsorption capacity for sulfur-based gas and can be molded into various modes. Moreover, since the physical property can be changed by mixing with the polyolefin resin, the sulfur gas adsorption resin composition of the present invention can be used for various applications and is useful. For example, when the resin composition of the present invention is molded and used in an all-solid-state lithium battery using a sulfide-based solid electrolyte membrane, the molded body adsorbs hydrogen sulfide generated inside, This is useful because the performance of the battery can be maintained for a long time.

Claims (11)

Aromatic vinyl having repeating units and repeating units derived from a diene monomer derived from an aromatic vinyl monomer - binder comprising a diene-based copolymer, and saw including an inorganic adsorbent which chemically adsorbs hydrogen sulfide, and
The inorganic adsorbent comprises a metal silicate containing at least one metal selected from copper, zinc, manganese, cobalt and nickel;
A kneaded body of a resin composition for sulfur-based gas adsorption (excluding a foam).   2. The aromatic vinyl monomer according to claim 1, wherein the aromatic vinyl monomer is selected from the group consisting of styrene, [alpha] -methyl styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, and vinyl naphthalene and mixtures thereof. Kneaded body.   The kneaded body according to claim 1 or 2, wherein the diene monomer is selected from linear or branched aliphatic diene or alicyclic diene having 4 to 10 carbon atoms and a mixture thereof.   The kneaded body according to claim 3, wherein the diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, and 1,3-pentadiene and mixtures thereof.   The kneaded body according to claim 1, wherein the copolymer is a styrene-butadiene copolymer. The kneaded body according to claim 1 , wherein the inorganic adsorbent is copper (II) silicate. The kneaded body according to any one of claims 1 to 6 , wherein the binder further includes a thermoplastic resin other than the aromatic vinyl-diene copolymer. The kneaded body according to claim 7 , wherein the thermoplastic resin is a polyolefin-based resin. The kneaded body according to claim 7 or 8 , wherein the aromatic vinyl-diene copolymer is 20% by weight or more based on the weight of the binder. The molded body for sulfur-based gas adsorption of a kneaded body according to any one of claims 1 to 9 , which has a film-like or sheet-like shape. Look including the kneading binder, and the inorganic adsorbent to chemically adsorb hydrogen sulfide containing diene copolymer, - aromatic vinyl having repeating units and repeating units derived from a diene monomer derived from an aromatic vinyl monomer And
The inorganic adsorbent comprises a metal silicate containing at least one metal selected from copper, zinc, manganese, cobalt and nickel;
The manufacturing method of the resin composition for sulfur type gas adsorption | suction which is not a foam.