JP6188545B2 - Laminate for sulfide gas adsorption - Google Patents

Description

  The present invention relates to a sulfide gas adsorption laminate including an adsorbent that adsorbs sulfide gas.

  Sulfide-based gases, such as hydrogen sulfide and mercaptans, are harmful gases that are flammable and toxic, 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.

  For example, an all-solid-state lithium battery using a sulfide-based solid electrolyte has a problem that when the sulfide-based solid electrolyte comes into contact with moisture, hydrogen sulfide is generated therein, and the performance is significantly deteriorated.

  Even in a light emitting diode (LED) device, there is a problem in that the LED element and peripheral members (particularly silver reflector parts) corrode, the initial output decreases over a long period, and / or the color tone changes. Further, in a factory where sulfide gas is generated, there is a problem that a metal member such as a circuit board for controlling a production machine, for example, a silver or copper terminal is corroded, and disconnection or a short circuit is likely to occur. Such a problem may also occur inside a display device or a communication device. In these, since metal members such as copper and silver are used, corrosion occurs in a place where sulfide-based gas exists. Furthermore, even in sewers and wastewater treatment facilities where the concentration of sulfide-based gas is high, there may be a problem that metal members and concrete materials are corroded and deteriorated.

  In order to cope with such a problem, an adsorbent for removing a sulfide-based gas as described in Patent Document 1 can be used. And in that case, since the inorganic adsorbent for sulfide gas is usually granular or powder as a single substance, like other inorganic adsorbents or inorganic absorbents, these are supported on fibers or the like, or resin It is conceivable to use it after kneading.

  The method of kneading into a resin generally uses a gas-absorbing performance lower than that of a method in which it is supported on a breathable fiber or the like. There is an advantage that it can be used for various purposes.

  However, when the adsorbent-containing resin composition is made into a film, as the amount of the adsorbent is increased, there are problems such as a decrease in film strength, a deterioration in surface roughness, a decrease in heat sealability, and a desorption of the adsorbent. May happen.

  On the other hand, Patent Document 2 discloses a laminate in which a reinforcing film is laminated on a moisture absorption layer obtained by kneading an inorganic moisture absorbent such as zeolite in LDPE. This laminate does not cause the above problems and can be used for various purposes.

JP 2011-104274 A JP-A-2005-280188

  When an adsorbent for sulfide gas is to be used in the vicinity of the above equipment or member, the adsorbent is adsorbed as in the invention described in Patent Document 2 in order to prevent desorption of the adsorbent. It is considered that it may be used as a laminate of a layer containing an agent and a layer not containing an adsorbent. However, it has been found that the adsorption performance is insufficient when a sulfide-based gas adsorbent is used in such a laminate.

  Then, this invention aims at providing the laminated body which can be used for various uses and has high adsorption | suction performance of sulfide type gas.

The present inventors have found that the above problems can be solved by the following means.
[1] A first skin layer including 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 and a binder that adsorb sulfide. A laminate for adsorbing sulfide-based gas having an adsorption layer.
[2] The laminate according to [1], wherein the first skin layer further includes a thermoplastic resin other than the aromatic vinyl-diene copolymer.
[3] The thermoplastic resin is a resin selected from the group consisting of polyolefin-based resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and mixtures thereof. Laminated body.
[4] Any one of [1] to [3], wherein the aromatic vinyl-diene copolymer is 10% by weight or more and 60% by weight or less based on the weight of the first skin layer. The laminated body as described in.
[5] Any one of [1] to [4], wherein the inorganic adsorbent includes a salt of at least one metal selected from copper, iron, zinc, manganese, cobalt, nickel, zirconium, and a lanthanoid element. The laminate according to item.
[6] The binder comprises a resin selected from the group consisting of a polyolefin-based resin, a saturated or unsaturated polyester, polyvinyl chloride, polystyrene, and derivatives thereof, and a mixture thereof. [1] to [5] The laminate according to any one of the above.
[7] The laminate according to any one of [1] to [6], which has a second skin layer containing a thermoplastic resin on a side opposite to the first skin layer of the adsorption layer.
[8] The thermoplastic resin of the second skin layer 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. Laminated body.
[9] The laminate according to [8], wherein the aromatic vinyl-diene copolymer is 10% by weight or more and 60% by weight or less based on the weight of the second skin layer.
[10] The thermoplastic resin of the second skin layer includes a resin selected from the group consisting of polyolefin resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and mixtures thereof. , [7] to [9] The laminate according to any one of [9].
[11] The laminate according to [10], wherein the aromatic vinyl-diene copolymer of the first and / or the second skin layer is a styrene-butadiene copolymer.

  The laminate of the present invention has good film strength, surface roughness, and heat sealability, can prevent the adsorbent from falling off, and has a high sulfide gas adsorption performance. Therefore, the laminate of the present invention can be used for various applications.

FIG. 1 (a) shows a two-layer laminate 10 comprising a first skin layer 1 and an adsorption layer 3, which is one embodiment of the present invention, and FIG. 1 (b) shows one embodiment of the present invention. A three-layer laminate comprising a first skin layer 1, a second skin layer 2, and an adsorption layer 3 is shown.

<Laminated body for sulfide gas adsorption>
The sulfide-based gas adsorption laminate of the present invention includes a first skin layer 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 a sulfide. And an adsorption layer containing an inorganic adsorbent and a binder. Here, the sulfide-based gas refers to a gas of a substance containing sulfur such as hydrogen sulfide gas, mercaptan-based gas, such as methanethiol and ethanethiol.

  By having a skin layer on at least one of the adsorbing layers, the laminate of the present invention can improve film strength, surface roughness, and heat sealability, and can prevent the adsorbent from falling off. In addition, since the skin layer includes an aromatic vinyl-diene copolymer, the laminate of the present invention can provide high sulfide gas adsorption performance.

  That is, as described above, when a sulfide-based adsorbent is used in the laminate of the adsorption layer and the skin layer as in the invention described in Patent Document 2, the adsorption performance becomes insufficient. In contrast, the present inventors have found that the adsorption performance of sulfide gas can be unexpectedly improved by including an aromatic vinyl-diene copolymer in the skin layer. Without being bound by theory, it is presumed that this is due to the high permeability of the sulfide-based gas to the aromatic vinyl-diene copolymer.

  FIG. 1 (a) shows a two-layer laminate 10 composed of a first skin layer 1 and an adsorption layer 3, which is an embodiment of the present invention. FIG. 1 (b) shows a three-layer laminate comprising a first skin layer 1, a second skin layer 2, and an adsorption layer 3, which is an embodiment of the present invention. Such a laminate may be formed into a bag shape by heat-sealing the skin layers.

(First skin layer)
The first skin layer contains an aromatic vinyl-diene copolymer. When the first skin layer contains the aromatic vinyl-diene copolymer, the sulfide-based gas easily reaches the adsorption layer through the first skin layer, so that the laminate of the present invention has the sulfide-based gas. It is considered that it has high adsorption performance.

  In addition, the first skin layer provides the laminate with high film strength, low surface roughness, and high heat sealability. Regarding the surface roughness, the arithmetic average roughness Ra of the first skin layer is preferably 2.00 μm or less, 1.50 μm or less, or 1.00 μm or less when measured in accordance with ISO4287.

  Regarding heat sealability, when the first skin layers are heat-sealed, the adhesion strength is a value measured according to the 90-degree peeling method according to JIS K6854-1, preferably 4.0 N / 15 mm or more. 6.0 N / 15 mm or more, or 8.0 N / 15 mm or more. The temperature at the time of heat sealing is preferably 80 to 150 ° C. depending on the material of the skin layer.

  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, Examples thereof include dicyclopentadiene, and one kind selected from these or two or more kinds can be used in combination. 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. .

  The first skin layer may be composed only of an aromatic vinyl-diene copolymer, but when considering moldability in inflation molding or T-die molding, the aromatic vinyl-diene copolymer may be used. It is preferable to mix and use the coalescence and other thermoplastic resins.

  That is, when the first skin layer is composed only of the above aromatic vinyl-diene copolymer, the softening temperature may be 80 ° C. or less. At this softening temperature, inflation molding or T-die molding is used. May be inappropriate. Therefore, by blending another thermoplastic resin with the aromatic vinyl-diene copolymer, the softening temperature is preferably 5 ° C. or higher, preferably 10 ° C. or higher, while maintaining a certain level of sulfide gas adsorption capacity. Or it can improve 30 degreeC or more. 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 aromatic vinyl-diene copolymer is 90 wt% or less, 80 wt% or less, 70 wt% or less, or 60 wt% or less from the viewpoint of moldability with respect to the weight of the first skin layer. In addition, it is preferably contained in the first skin layer in an amount of 10%, 20%, 25%, 30%, or 40% by weight or more from the viewpoint of sulfide gas permeability. It is preferable that In particular, when it is contained in the first skin layer in excess of 20% by weight or 30% by weight or more, the effect is remarkably exhibited.

  Examples of the thermoplastic resin other than the aromatic vinyl-diene copolymer that may be contained in the first skin layer include polyolefin resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and These mixtures are mentioned.

  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.

  The thickness of the first skin layer is preferably 5 μm or more, 10 μm or more, or 20 μm or more from the viewpoint of obtaining appropriate moldability and elasticity, and is 100 μm or less, 70 μm or less, 50 μm or less, or 40 μm or less. Is preferred.

(Second skin layer)
The second skin layer includes a thermoplastic resin. The second skin layer may be made of the same material as the first skin layer, or may be made of a different material, that is, the second skin layer is made of aromatic vinyl as a thermoplastic resin. A diene copolymer may or may not be included.

  Examples of the thermoplastic resin that can be used for the second skin layer include the above aromatic vinyl-diene copolymers and thermoplastic resins that can be used for the first skin layer. The second skin layer may be composed of, for example, a polyolefin-based resin without including the aromatic vinyl-diene copolymer, and the second skin layer may be used as an adhesive surface to the object of use. When the second skin layer contains an aromatic vinyl-diene copolymer, the content can be in the same range as that used in the first skin layer. The thickness of the second skin layer can also be in the same range as the thickness of the first skin layer.

(Adsorption layer)
The adsorption layer includes an inorganic adsorbent that adsorbs sulfide and a binder. As the binder, the same resin as the thermoplastic resin that can be used for the second skin layer can be used, and the above aromatic vinyl-diene copolymer may be used.

  The sulfide gas adsorbent used in the present invention is an inorganic adsorbent that chemically and / or physically adsorbs sulfide gas. Preferably, the sulfide-based gas adsorbent used in the present invention is a chemical adsorbent, which adsorbs by reacting with sulfides on its surface to form sulfides, adsorbing sulfides by coordination bonds, etc. It is an inorganic adsorbent having an adsorption mechanism. As the sulfide-based gas adsorbent, a physical adsorbent can be used, and examples thereof include aluminum oxide, quicklime, silica gel, and an inorganic molecular sieve. Examples of inorganic molecular sieves include, but are not limited to, aluminosilicate minerals, clays, porous glass, microporous activated carbon, zeolite, activated carbon, or compounds having an open structure capable of diffusing small molecules such as water. Can be mentioned.

  This inorganic adsorbent is 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more or 10 parts by mass with respect to 100 parts by mass of the binder resin in consideration of kneadability and adsorption performance. It is preferable to include the above, preferably 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 or salts 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. As the _{silicate, M 2 O · nSiO 2 ·} xH 2 O ( wherein, M in the formula represents a monovalent alkali metal, n represents 1 or more, and x is 0 or more.) Formula Kay Acid alkali salts can be mentioned. 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 sulfide-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 with respect to methyl mercaptan per 1 g of adsorbent at 25 ° C., And / or 20 ml / g or more, 40 ml / g or more, or 60 ml / g or more with respect to hydrogen sulfide.

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.

  The thickness of the adsorption layer is preferably 10 μm or more, 20 μm or more, or 30 μm or more from the viewpoint of adsorption performance, moldability, and elasticity, and is 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, or 50 μm or less. It is preferable.

<Method for producing sulfide-based gas-adsorbing laminate>
The sulfide-based gas adsorption laminate of the present invention can be produced by subjecting the material of each of the above layers to various molding methods, for example, extrusion molding such as press molding, inflation method, T-die method, and coextrusion. . Among these, the molding by the inflation method or the T-die method is particularly preferable.

  Moreover, after forming an adsorption layer into a film by an inflation method, a T-die method, a solvent casting method, a press, etc., and forming a first skin layer and optionally a second skin layer by these methods, the adsorption layer The laminate of the present invention can also be produced by laminating. In this case, each layer can be formed at a temperature of 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, and 220 ° C. or lower, 200 ° C. or lower, or 180 ° C. or lower, depending on the material used. .

  For kneading the materials used in each layer, for example, a batch kneader such as a kneader, a Banbury mixer, a mixing roll, or a continuous kneader such as a biaxial kneader can be used. In this case, kneading can be performed at a temperature of 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, and 220 ° C. or lower, 200 ° C. or lower, or 180 ° C. or lower, depending on the material used.

<Usage method of laminate for sulfide gas adsorption>
The laminate for adsorbing sulfide-based gas of the present invention is used in an all solid-state lithium battery using a sulfide-based solid electrolyte to adsorb internally generated hydrogen sulfide and maintain the battery performance for a long period of time. Can do. Further, by disposing the laminate of the present invention in the vicinity of the LED element or behind the LED package or lead frame, corrosion of peripheral members such as the LED element and the silver reflector component can be prevented. By using the laminate of the present invention in the vicinity of equipment used in a place where sulfide gas is generated, for example, a circuit board for controlling a production machine in a factory, and a display device and a communication device used in the factory, Corrosion of a metal member, for example, a silver or copper terminal can be prevented. Furthermore, by disposing the laminate of the present invention in the vicinity of metal members and concrete materials such as sewers and wastewater treatment facilities where the concentration of sulfide gas is high, corrosion of them can be prevented.

  In the above case, the laminate can be attached to the object to be used by heat-sealing the skin layer of the laminate of the present invention. Moreover, the laminated body of this invention is formed in a bag shape, and board | substrate components containing silver and copper, for example are put in this bag, and the corrosion of board | substrate components etc. can be prevented by storing or transporting.

  Furthermore, the laminate of the present invention can be used as a food packaging film described in JP-A No. 62-64737. 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, it is possible to adsorb the generated hydrogen sulfide by constituting the retort pouch using the laminate of the present invention or enclosing the laminate of the present invention inside, so Deterioration of flavor can be suppressed.

1. Production of skin layer film Table 1 shows SBR (ASAPrene 432, manufactured by Asahi Kasei Chemicals Corporation) as an aromatic vinyl-diene copolymer, and polypropylene (FL02A, manufactured by Nippon Polypro Co., Ltd.) as a polyolefin resin. The mixture was kneaded with a Banbury mixer at a rotation speed of 100 rpm and a cylinder temperature of 160 ° C. for 10 minutes. Then, the kneaded body was formed into a film having a thickness of 50 μm by a T die method using a 160 ° C. T die.

2. Preparation of film for adsorption layer 90 parts by mass of polypropylene (FL02A, manufactured by Nippon Polypro Co., Ltd.) as a binder and 10 parts by mass of a copper (II) silicate-based adsorbent (Kesmon NS-20C, Toagosei Co., Ltd.) as an inorganic adsorbent Were kneaded with a Banbury mixer at a rotation speed of 100 rpm and a cylinder temperature of 160 ° C. for 10 minutes. This was formed into a film having a thickness of 50 μm by a T die method using a 160 ° C. T die.

3. Production of Laminate The above-mentioned skin layer film was superposed on both sides of the above-mentioned adsorption film and heat-pressed to produce a laminate comprising three layers of films. The thickness of the laminated body after pressing was 80 μm, the skin layers were 30 μm each, and the adsorption layer was 20 μm.

4). Evaluation of adsorption amount of hydrogen sulfide The laminate was cut into 10 mm × 10 mm and placed in an aluminum pack. 200 ml of 100 ppm hydrogen sulfide standard gas (remainder: nitrogen) was injected into the aluminum pack, and the amount of hydrogen sulfide in the aluminum pack after 24 hours was measured by gas chromatography. evaluated.

5. Evaluation of seal strength A strip-like film obtained by cutting the above laminate into 15 mm x 70 mm was prepared, and two sheets of these films were overlapped, and heat sealed for 0.7 seconds under conditions of 130 ° C and 0.2 MPa. A sample for measurement was prepared. This sample was subjected to a 90 ° peel test in accordance with JIS K 6854-1, using a tensile tester (Toyo Seiki Seisakusho, Strograph VE100). Here, the peeling time was 300 mm / min, and the distance between chucks was 50 mm.

6). Results These results are shown in Table 1 below.

  As is apparent from Table 1, the amount of the sulfide-based gas adsorbed can be increased as the amount of the aromatic vinyl-diene copolymer contained in the skin layer is increased. Further, it was found that when the amount of the aromatic vinyl-diene copolymer is more than a certain amount, the heat seal strength of the laminate can be increased. Further, it has been found that when the content of the aromatic vinyl-diene copolymer is more than 20% by weight or 30% by weight or more, the adsorption amount of the sulfide-based gas can be increased remarkably.

  In the above embodiment, when the SBR was 70 parts by mass, the skin layer could not be formed by the T-die method. However, if the skin layer is formed by the pressing method as in the following reference example and laminated with the adsorption layer, it is clear that the skin layer can be composed of only SBR.

7). Reference Example In the following reference example, it will be shown how the adsorption amount of sulfide-based gas by the adsorption layer changes by using various resins for the binder of the adsorption layer. This experiment suggests that the aromatic vinyl-diene copolymer has an unexpectedly high sulfide gas permeability.

  90 parts by mass of the binder resin listed in Table 2 below and 10 parts by mass of Kesmon NS-20C (manufactured by Toagosei Co., Ltd.), which is a sulfide-based gas adsorbent, are 10 at a rotational speed of 50 rpm and a temperature of 140 ° C. A kneaded body containing an adsorbent was obtained. These kneaded bodies were pressed with a press machine at a temperature of 140 ° C. and a pressure of 20 MPa for 30 seconds to obtain a film for sulfur-based gas adsorption of Reference Examples 1 to 8 having a thickness of 50 μm.

  Cut this film into 25mm x 10mm, put it in an aluminum pack, inject a certain amount of 100ppm hydrogen sulfide standard gas (remainder: nitrogen), and the amount of hydrogen sulfide in the aluminum pack 24 hours later is gas chromatographed in the aluminum pack. The amount of adsorption was obtained by measuring the amount of hydrogen sulfide.

  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 Reference Examples 1 to 4 in which the SBR contains an adsorbent, the hydrogen sulfide adsorption amount by the above measurement method is all high values of 10.0 μL / mg · 24 h or more, but butadiene rubber (BR), polyethylene In Reference Examples 5 to 8 containing an adsorbent in (PE), polystyrene (PS), and polypropylene (PP), the hydrogen sulfide adsorption amount is very low.

  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.

  The laminate of the present invention has various film uses because it has good film strength, surface roughness, and heat sealability, can prevent the adsorbent from falling off, and has high sulfide gas adsorption performance. Can be used.

DESCRIPTION OF SYMBOLS 1 1st skin layer 2 2nd skin layer 3 Adsorption layer 10 Laminated body for sulfide type gas adsorption

Claims (11)

A first skin layer 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 adsorption layer comprising an inorganic adsorbent and a binder adsorbing sulfide A laminate for sulfide gas adsorption.   The laminate according to claim 1, wherein the first skin layer further contains a thermoplastic resin other than the aromatic vinyl-diene copolymer.   The laminate according to claim 2, wherein the thermoplastic resin is a resin selected from the group consisting of polyolefin-based resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and mixtures thereof. .   The laminate according to any one of claims 1 to 3, wherein the aromatic vinyl-diene copolymer is 10 wt% or more and 60 wt% or less with respect to the weight of the first skin layer. .   The laminate according to any one of claims 1 to 4, wherein the inorganic adsorbent includes a salt of at least one metal selected from copper, iron, zinc, manganese, cobalt, nickel, zirconium, and a lanthanoid element. body.   6. The binder according to any one of claims 1 to 5, wherein the binder comprises a resin selected from the group consisting of polyolefin-based resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and mixtures thereof. The laminated body as described in.   The laminate according to any one of claims 1 to 6, further comprising a second skin layer containing a thermoplastic resin on a side opposite to the first skin layer of the adsorption layer.   The laminate according to claim 7, wherein the thermoplastic resin of the second skin layer 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 laminate according to claim 8, wherein the aromatic vinyl-diene copolymer is 10 wt% or more and 60 wt% or less based on the weight of the second skin layer.   The thermoplastic resin of the second skin layer comprises a resin selected from the group consisting of polyolefin resins, saturated or unsaturated polyesters, polyvinyl chloride, polystyrene, and derivatives thereof, and mixtures thereof. The laminated body as described in any one of 7-9.   The laminate according to claim 8 or 9, wherein the aromatic vinyl-diene copolymer of the first and / or second skin layer is a styrene-butadiene copolymer.

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