WO2017078103A1 - イソブチレン系共重合体を含む樹脂組成物及び成形体 - Google Patents
イソブチレン系共重合体を含む樹脂組成物及び成形体 Download PDFInfo
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- WO2017078103A1 WO2017078103A1 PCT/JP2016/082682 JP2016082682W WO2017078103A1 WO 2017078103 A1 WO2017078103 A1 WO 2017078103A1 JP 2016082682 W JP2016082682 W JP 2016082682W WO 2017078103 A1 WO2017078103 A1 WO 2017078103A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/10—Bag-type containers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to a resin composition containing an isobutylene copolymer and a molded body.
- laminates having a gas barrier layer and a flexible resin layer made of an ethylene-vinyl alcohol copolymer or polyamide are widely used.
- NR natural rubber
- IIR butyl rubber
- vinyl chloride is used as a material for medical infusion bags because flexibility and gas barrier properties are required.
- IIR is used as a material for a tire tube because it requires a high gas barrier property and flexibility.
- IIR is excellent in flexibility [durometer hardness (type A) of about 65] and gas barrier property [OTR 4000 cc ⁇ 20 ⁇ m / (m 2 ⁇ day ⁇ atm)], it is flexible in molded products using IIR. In order to achieve this, a complicated vulcanization process is required after molding. Ethylene-vinyl alcohol copolymers and polyamides are excellent in gas barrier properties but have insufficient flexibility. Therefore, laminates of barrier layers made of these resins and flexible resin layers are used as food packages. However, as a result, there are limitations and complications in the molding process. Since NR is not so high in gas barrier properties, when it is used as a material for container packing, it is disadvantageous in terms of long-term storage of contents. In addition, molded articles using vinyl chloride are concerned about adverse environmental effects due to the generation of hydrogen chloride gas during incineration.
- SEBS Styrene-Ethylene / Butylene-Styrene Triblock Copolymer
- SEPS Styrene-Ethylene / Propylene-Styrene Triblock Copolymer
- gas barrier property may be insufficient depending on the application.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a resin composition that is excellent in flexibility and gas barrier properties and can be stably produced over a long period of time. Moreover, it aims at providing the molded object using the said resin composition.
- a halogen scavenger (C) the mass ratio (B / A) of the ethylene-vinyl alcohol copolymer (B) to the isobutylene copolymer (A) is 20/80 to 50/50, Provided is a resin composition containing 0.01 to 1 part by mass of a halogen scavenger (C) with respect to 100 parts by mass as a total of the copolymer (A) and the ethylene-vinyl alcohol copolymer (B). It is solved by.
- the halogen scavenger (C) is a layered inorganic compound having exchangeable ions, and it is more preferable that the layered inorganic compound is hydrotalcite. It is also preferred that the halogen atom contained in the isobutylene copolymer (A) is a chlorine atom. It is also preferred that the isobutylene copolymer (A) is a block copolymer having a polymer block (a1) composed of vinyl aromatic monomer units and a polymer block (a2) composed of isobutylene units.
- the resin composition contains 0.001 to 0.2 parts by mass of the carboxylic acid metal salt (D) with respect to 100 parts by mass of the total amount of the isobutylene copolymer (A) and the ethylene-vinyl alcohol copolymer (B). It is preferable to include.
- a molded body having a layer made of the resin composition is a preferred embodiment of the present invention.
- the molded body is suitably used for food packages, container packings, medical infusion bags, and tire tubes.
- the resin composition of the present invention is excellent in flexibility and gas barrier properties, and even when produced over a long period of time, the resin is prevented from being crosslinked, and thus can be produced stably.
- a molded body using the resin composition is excellent in flexibility and gas barrier properties and has a good appearance (an appearance with few aggregates derived from a halogen scavenger).
- the resin composition of the present invention contains an isobutylene copolymer (A) containing a halogen atom, an ethylene-vinyl alcohol copolymer (B) and a halogen scavenger (C), and contains an isobutylene copolymer (A ) Is a mass ratio (B / A) of the ethylene-vinyl alcohol copolymer (B) to 20/80 to 50/50, and the isobutylene copolymer (A) and the ethylene-vinyl alcohol copolymer (B).
- the halogen scavenger (C) is contained in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass in total.
- the isobutylene copolymer (A) containing a halogen atom contained in the resin composition of the present invention may be a copolymer having an isobutylene unit content of 20% by mass or more.
- the monomer is not particularly limited.
- the block copolymer which has a polymer block (a1) which consists of a vinyl aromatic monomer unit, and a polymer block (a2) which consists of an isobutylene unit as an isobutylene-type copolymer (A) is preferable.
- the block copolymer may have at least one polymer block (a1) and at least one polymer block (a2) in the molecule, and the structure is not particularly limited.
- the block copolymer may have a linear chain structure, a branched chain structure branched into two or more, and a star-shaped molecular chain form.
- the block copolymer used as the isobutylene copolymer (A) is typically a diblock structure represented by a1-a2, a triblock represented by a1-a2-a1 or a2-a1-a2.
- the structure is a tetrablock structure represented by a1-a2-a1-a2, a polyblock structure in which a total of five or more a1 and a2 are linearly bonded, or a mixture thereof.
- the isobutylene copolymer (A) can be used alone or in combination of two or more.
- the vinyl aromatic monomer unit which is a constituent unit of the polymer block (a1) is a unit derived from a vinyl aromatic monomer by addition polymerization.
- the vinyl aromatic monomer those containing no halogen atom are preferable from the viewpoint of suppressing cross-linking during long-term production.
- styrenes such as styrene, ⁇ -methylstyrene, 2-methylstyrene, 4-methylstyrene;
- vinyl group-containing aromatic compounds such as vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene.
- the vinyl aromatic monomer unit constituting the polymer block (a1) may be only one type or two or more types. Among these, it is preferable that a polymer block (a1) consists of a styrene unit.
- the lower limit of the number average molecular weight of the polymer block (a1) is preferably 1000, more preferably 2000.
- the upper limit of the number average molecular weight of the polymer block (a1) is preferably 400,000, and more preferably 200000.
- the isobutylene unit which is a constituent unit of the polymer block (a2), is a unit derived from isobutylene by addition polymerization (—C (CH 3 ) 2 —. CH 2- ).
- the lower limit of the number average molecular weight of the polymer block (a2) is preferably 10,000. Thereby, the gas barrier property of the resin composition obtained becomes especially favorable.
- the upper limit of the number average molecular weight of the polymer block (a2) is preferably 400,000. When the number average molecular weight of the polymer block (a2) is in the above range, the moldability and workability of the resulting resin composition are improved.
- the ratio of the polymer block (a1) and the polymer block (a2) contained in the block copolymer used as the isobutylene copolymer (A) may be appropriately determined.
- the lower limit of the content of the polymer block (a1) therein is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass with respect to the total mass of the isobutylene copolymer (A).
- the content of the polymer block (a1) is not less than the above lower limit, mechanical properties such as strength of the obtained resin composition are improved.
- the upper limit of the content of the polymer block (a1) is preferably 80% by mass, more preferably 70% by mass, and still more preferably 50% by mass with respect to the total mass of the isobutylene copolymer (A).
- content of a polymer block (a1) is below said upper limit, melt viscosity does not become high too much and the moldability and workability of the resin composition obtained improve.
- the some polymer block (a1) is contained in the isobutylene-type copolymer (A)
- those total amount be content of a polymer block (a1).
- the isobutylene copolymer (A) contained in the resin composition of the present invention contains a halogen atom.
- the halogen atom is considered to be derived from the polymerization catalyst used in the production of the isobutylene copolymer (A), and is mainly contained at the end of the isobutylene copolymer (A).
- Examples of the halogen atom contained in the isobutylene copolymer (A) include chlorine, bromine, fluorine, iodine and the like, and among them, chlorine is often contained.
- the content of halogen atoms in the isobutylene copolymer (A) is usually 0.005 to 3.000% by mass.
- the halogen atom in the isobutylene copolymer (A) can be analyzed using an ion chromatograph.
- the lower limit of the number average molecular weight of the isobutylene copolymer (A) is preferably 12000, more preferably 30000. When the number average molecular weight is not less than the above lower limit, the mechanical properties such as strength and elongation of the obtained resin composition are improved.
- the upper limit of the number average molecular weight of the isobutylene copolymer (A) is preferably 600000, more preferably 400000. When the number average molecular weight of the isobutylene copolymer (A) is not more than the above upper limit, the moldability and workability of the resulting resin composition are improved.
- Melt flow rate of isobutylene copolymer (A) (measured by the method described in ASTM D1238 under the conditions of a temperature of 230 ° C. and a load of 2160 g, hereinafter “melt flow rate” may be referred to as “MFR”) Is preferably 0.05 g / 10 minutes, more preferably 2.5 g / 10 minutes, and even more preferably 5.0 g / 10 minutes.
- the upper limit of the MFR of the isobutylene copolymer (A) is preferably 100 g / 10 minutes, more preferably 50 g / 10 minutes, and further preferably 20 g / 10 minutes. When MFR is in the above range, the moldability and workability of the resulting resin composition are improved.
- a functional group may be introduced into the isobutylene copolymer (A) by any method as long as the effects of the present invention are not impaired.
- functional groups that can be introduced include ether groups such as hydroxyl groups, amino groups, alkylamino groups, epoxy groups, alkoxyl groups, ester groups such as carboxyl groups, alkoxycarbonyl groups, acyloxyl groups, carbamoyl groups, alkylcarbamoyl groups, Examples thereof include an amide group such as an acylamino group and a group having a dicarboxylic anhydride structure such as a maleic anhydride residue.
- the production method of the isobutylene copolymer (A) is not particularly limited. However, when producing the block copolymer, the polymerization operation of the vinyl aromatic monomer and the polymerization of isobutylene are carried out in an inert solvent using a polymerization initiator. The method of manufacturing by performing operation in steps in arbitrary orders is preferable.
- the polymerization initiator used in that case is preferably a Lewis acid and a combination system with an organic compound capable of generating a cationic polymerization active species by the Lewis acid.
- a halogen atom-containing compound such as titanium tetrachloride, tin tetrachloride, boron trichloride, aluminum chloride is used.
- the isobutylene copolymer (A) can be produced efficiently.
- a halogen atom-containing compound is used as the Lewis acid, it is known that the halogen atom is contained at the terminal of the isobutylene copolymer (A).
- the organic compound capable of generating a cationic polymerization active species by Lewis acid include, for example, bis (1-methoxy-1-methylethyl) benzene, bis (1-acetoxy-1-methylethyl) benzene, bis (1-chloro- 1-methylethyl) benzene and the like can be used.
- organic solvents such as hexane, cyclohexane, methylcyclohexane, methyl chloride, and methylene chloride can be used.
- isobutylene copolymer (A) for example, as a polymerization initiator system, one or two functional groups capable of generating the above-described Lewis acid and cationic polymerization active species are included in the molecule, or Using three organic compounds, isobutylene is added to the reaction system and polymerized to form a polymer block (a2), and then a vinyl aromatic monomer is polymerized to form a polymer block (a1). The method is preferred.
- EVOH (B) contained in the resin composition of the present invention is a copolymer mainly composed of ethylene units and vinyl alcohol units, and is obtained by saponifying vinyl ester units in the ethylene-vinyl ester copolymer.
- Is. EVOH (B) used in the present invention is not particularly limited, and known ones used for melt molding can be used. EVOH (B) can be used alone or in combination of two or more.
- the upper limit of the content of ethylene units in EVOH (B) is preferably 65 mol%, more preferably 60 mol%, and even more preferably 48 mol%. If the above upper limit is exceeded, the gas barrier properties of the resulting resin composition may be reduced.
- the degree of saponification of EVOH (B) is not particularly limited, it is preferably 90 mol% or more, more preferably 95 mol% or more, from the viewpoint of maintaining the gas barrier property of the resulting resin composition. More preferably, it is 99 mol% or more.
- the MFR of EVOH (B) (measured by the method described in ASTM D1238 under the conditions of a temperature of 210 ° C. and a load of 2160 g) is preferably 0.5 g / 10 minutes as the lower limit, and 1.0 g / 10 minutes. Is more preferable, and 2.0 g / 10 min is even more preferable.
- the upper limit of MFR is preferably 100 g / 10 minutes, more preferably 50 g / 10 minutes, and even more preferably 25 g / 10 minutes. When MFR is in the above range, the moldability and workability of the resulting resin composition are improved.
- EVOH (B) may have other structural units in addition to the ethylene unit, the vinyl alcohol unit, and the vinyl ester unit.
- other structural units include units derived from vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( ⁇ -methoxy-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane. Of these, units derived from vinyltrimethoxysilane or vinyltriethoxysilane are preferred.
- EVOH (B) is an olefin such as propylene and butylene; an unsaturated carboxylic acid such as (meth) acrylic acid and methyl (meth) acrylate or an ester thereof; N-vinyl, as long as the object of the present invention is not hindered. It may have units derived from vinylpyrrolidone such as pyrrolidone.
- the content of units other than the ethylene unit, vinyl alcohol unit and vinyl ester unit is preferably 10 mol% or less, more preferably 5 mol% or less, based on all the structural units.
- EVOH (B) can be produced, for example, by producing an ethylene-vinyl ester copolymer according to a known method and then saponifying it.
- the ethylene-vinyl ester copolymer is, for example, a radical such as benzoyl peroxide or azobisisobutyronitrile under pressure in an organic solvent such as methanol, t-butyl alcohol, or dimethyl sulfoxide. It is obtained by polymerizing using a polymerization initiator.
- vinyl ester vinyl acetate, vinyl propionate, vinyl pivalate and the like can be used, and among these, vinyl acetate is preferable.
- An acid catalyst or an alkali catalyst can be used for the saponification of the ethylene-vinyl ester copolymer.
- the lower limit of the mass ratio (B / A) of EVOH (B) to the isobutylene copolymer (A) in the resin composition of the present invention needs to be 20/80, preferably 25/75, 30 / 70 is more preferable.
- the mass ratio (B / A) is less than the above lower limit, the gas barrier property of the resin composition is lowered.
- the upper limit of the mass ratio (B / A) needs to be 50/50, preferably 45/55, and more preferably 40/60.
- the mass ratio (B / A) exceeds the above upper limit, the flexibility of the resin composition becomes insufficient.
- the halogen scavenger (C) contained in the resin composition of the present invention only needs to have a halogen scavenging ability.
- a layered inorganic compound having exchangeable ions; magnesium oxide, calcium hydroxide, magnesium hydroxide And alkaline earth metal compounds such as calcium carbonate; zinc oxide; lithium carbonate and the like.
- the halogen scavenger (C) is a layered inorganic compound having exchangeable ions.
- the layered inorganic compound include clay minerals; layered polysilicic acid; layered silicates; layered double hydroxides; layered phosphates; Examples thereof include acid salts; layered manganese oxides; layered cobalt oxides, among which clay minerals are preferable.
- Examples of the clay mineral include hydrotalcite, zeolite, mica, vermiculite, montmorillonite, beidellite, saponite, hectorite, and stevensite.
- the clay mineral may be synthetic clay or natural clay.
- hydrotalcite and zeolite are preferable as the clay mineral, and the former is more preferable.
- Examples of the hydrotalcite include those represented by the following general formula (I), and examples of the zeolite include those represented by the following formula (II).
- the lower limit of the content of the halogen scavenger (C) in the resin composition of the present invention is 0.01 part by mass with respect to 100 parts by mass of the total amount of the isobutylene copolymer (A) and EVOH (B). Is necessary and is preferably 0.025 parts by mass.
- the content of the halogen scavenger (C) is less than the above lower limit, the resin rapidly crosslinks when the resin composition is produced over a long period of time.
- the upper limit of the content of the halogen scavenger (C) is required to be 1 part by mass with respect to 100 parts by mass of the total amount of the isobutylene copolymer (A) and EVOH (B). It is preferably 8 parts by mass.
- the content of the halogen scavenger (C) exceeds the above upper limit, the number of aggregates derived from the halogen scavenger in the resulting molded article increases and the appearance is impaired.
- the mass ratio [(C) / halogen atom] of the halogen scavenger (C) to the halogen atom contained in the isobutylene copolymer (A) is preferably 0.10 or more. , 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.25 or more. Further, the mass ratio [(C) / halogen atom] is preferably 10 or less, more preferably 2 or less, and further preferably 1 or less.
- the main feature of the resin composition of the present invention is that it contains the halogen scavenger (C) described above.
- C halogen scavenger
- the inhibitory effect of the crosslinking of the present invention is not only the suppression of gelation that occurs in a short time, but also suppresses the progress of the crosslinking reaction when produced over a long period of time.
- the total amount of isobutylene copolymer (A), EVOH (B) and halogen scavenger (C) in the resin composition of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass. % Or more is more preferable.
- the resin composition of the present invention further comprises 0.001 to 0.3 parts by mass of a carboxylic acid metal salt (D) with respect to 100 parts by mass of the total amount of the isobutylene copolymer (A) and EVOH (B). Is preferred. Thereby, even if there is little content of the halogen scavenger (C) in a resin composition, the rapid bridge
- the carboxylic acid constituting the carboxylic acid metal salt (D) is preferably a carboxylic acid having 1 to 30 carbon atoms, specifically, acetic acid, stearic acid, lauric acid, montanic acid, behenic acid, octylic acid, Examples thereof include sebacic acid, ricinoleic acid, myristic acid, palmitic acid, etc. Among them, acetic acid and stearic acid are particularly preferable.
- the metal constituting the carboxylic acid metal salt (D) an alkaline earth metal is suitable, and specific examples include magnesium and calcium.
- the resin composition of this invention may contain compounds, such as metal salts other than carboxylic acid metal salt (D), and an acid, from a viewpoint of heat stability or a viscosity adjustment.
- examples of such compounds include carboxylic acids, phosphoric acid compounds, and boron compounds. Specific examples include the following. In addition, these compounds may be previously contained in the isobutylene copolymer (A) or EVOH (B).
- Carboxylic acid oxalic acid, succinic acid, benzoic acid, citric acid, acetic acid, lactic acid, etc.
- Phosphoric acid compound Various acids such as phosphoric acid and phosphorous acid and their salts Boron compounds: Boric acids, boric acid esters, boric acid Salt, borohydride, etc.
- the resin composition may contain various additives other than those described above as long as the effects of the present invention are not impaired.
- additives include antioxidants, plasticizers, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, nucleating agents, flame retardants, isobutylene copolymers (A) and EVOH ( Examples thereof include polymers other than B).
- the content of components other than the isobutylene copolymer (A), EVOH (B) and the halogen scavenger (C) in the resin composition is preferably 50% by mass or less, more preferably 20% by mass or less. A mass% or less is more preferable.
- Polymers other than isobutylene copolymer (A) and EVOH (B) contained in the resin composition include EPR (ethylene-propylene rubber), EPDM (ethylene-propylene-diene rubber), NR (natural Rubber), isoprene rubber, butadiene rubber, IIR (butyl rubber), and the like; and thermoplastic resins such as polyethylene, polypropylene, polybutene, polyisobutylene, polyamide, and polyester.
- the upper limit of the content of the polymer other than the isobutylene copolymer (A) and EVOH (B) contained in the resin composition is preferably 20% by mass and more preferably 10% by mass with respect to all polymer components. 5 mass% is more preferable.
- the lower limit of the total amount of isobutylene copolymer (A) and EVOH (B) with respect to all polymer components in the resin composition is preferably 80% by mass, more preferably 90% by mass, and 95% by mass. Further preferred.
- the method for preparing the resin composition of the present invention is not particularly limited, but it is preferably prepared by adding the halogen scavenger (C) to the isobutylene copolymer (A) and EVOH (B) and then melt-kneading.
- C halogen scavenger
- Kneaders, kneaders, extruders, mixing rolls, Banbury mixers and the like can be used.
- the temperature at the time of melt kneading is usually 110 to 300 ° C.
- the halogen scavenger (C) may be previously contained in the isobutylene copolymer (A) or EVOH (B).
- the molded object of this invention consists of the said resin composition.
- the resin composition of the present invention has thermoplasticity, it can be molded using a normal molding method or molding apparatus used for general thermoplastic polymers.
- a normal molding method or molding apparatus used for general thermoplastic polymers for example, any method such as injection molding, extrusion molding, press molding, blow molding, calendar molding, or vacuum molding can be employed.
- Molded products comprising the resin composition produced by such a method include molds, pipes, sheets, films, tubes, disks, rings, bags, bottles, strings, fibers.
- a wide variety of shapes are included.
- a preferable shape of the molded body is a film shape or a tube shape.
- the molded body having a layer made of the resin composition is preferable as the molded body.
- the molded body may be a single-layer structure or a laminate as long as it has a layer made of the resin composition. From the viewpoint of improving moisture resistance, mechanical properties, and the like, a laminate having a layer made of the resin composition is preferable as the molded body.
- the laminate has at least one layer made of the resin composition and at least one layer made of another material.
- Other materials may be appropriately selected according to required characteristics and intended use.
- Other materials are preferably thermoplastic resins, for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, polyolefin such as polypropylene; ethylene-vinyl acetate copolymer Examples thereof include thermoplastic polymers such as polymers, ethylene-acrylic acid ester copolymers, polystyrene, vinyl chloride resins and vinylidene chloride resins; ionomers and the like.
- the thermoplastic resin may be an isobutylene copolymer (A) or EVOH (B).
- an adhesive layer or an adhesive may be interposed between the resin composition layer and a layer made of another material.
- the adhesive layer or adhesive an acid anhydride-modified product of a diene polymer; a polyolefin acid anhydride-modified product; a mixture of a polymer polyol and a polyisocyanate compound can be used.
- the layer made of polyolefin is a polyolefin layer
- the interlaminar adhesiveness is excellent even without an adhesive layer or an adhesive, and therefore the significance of interposing the adhesive layer or the adhesive is small.
- a known method such as co-extrusion, co-injection or extrusion coating can also be used.
- the thickness of the molded product of the present invention is preferably 50 to 5000 ⁇ m.
- the thickness of the layer made of the resin composition of the present invention is preferably 5 to 500 ⁇ m, and the thickness of the layer made of another material is preferably 45 to 4500 ⁇ m.
- the molded body Since the molded body is excellent in balance between gas barrier properties and flexibility, it can be used as daily necessities, packaging materials, machine parts and the like that require these properties.
- Examples of applications in which the features of the molded body are particularly effective include food packaging, container packing, medical infusion bags, tire tubes, shoe cushions, containers, bag-in-box inner bags, organic liquids Examples include storage tanks, pipes for transporting organic liquids, and hot water pipes for heating (such as hot water pipes for floor heating).
- particularly preferred applications are food packages, container packings, medical infusion bags, and tire tubes.
- A-4 “SIBSTAR 062T” manufactured by Kaneka, styrene-isobutylene-styrene block copolymer MFR 10 g / 10 min (230 ° C., load 2160 g); content of polymer block composed of styrene units 24 mass%, number average molecular weight 60000 Content of polymer block composed of isobutylene units is 77% by mass; chlorine atom content is 0.11% by mass
- A-5 “Taftec H1041” manufactured by Asahi Kasei Co., Ltd., styrene-ethylene-butylene-styrene block copolymer MFR 5.0 g / 10 min, content of polymer block consisting of styrene units 30% by mass; polymer block consisting of butadiene units Content of 70 mass%; chlorine atom content of 0.00 mass%
- MFR Melt flow rate
- durometer hardness measurement According to JIS K 6253-3, durometer hardness was measured using a durometer hardness meter (type A) manufactured by Shimadzu Corporation in a state where two injection pieces to be described later were stacked to a thickness of 8 mm.
- Oxygen permeability (OTR) After conditioning the monolayer film described below under the condition of 20 ° C./65% RH, using an oxygen transmission rate measuring device (“OX-Tran 2/20” manufactured by Modern Control), the condition of 20 ° C./65% RH below, oxygen permeability (OTR) was measured according to the method described in JIS K 7126 (isobaric method).
- Synthesis example 1 [Production of Isobutylene Copolymer A-1] In a reactor equipped with a stirrer substituted with nitrogen, a mixed solvent consisting of 1060 parts by mass of methylene chloride and 920 parts by mass of methylcyclohexene, 2.7 parts by mass of titanium tetrachloride and 1,4-bis (1-methoxy-1 -Methylethyl) A polymerization initiator consisting of 0.91 part by mass of benzene was charged and cooled to -65 ° C., and then 150 parts by mass of isobutylene was charged and polymerized for 4 hours.
- a mixed solvent consisting of 1060 parts by mass of methylene chloride and 920 parts by mass of methylcyclohexene, 2.7 parts by mass of titanium tetrachloride and 1,4-bis (1-methoxy-1 -Methylethyl)
- a polymerization initiator consisting of 0.91 part by mass of benzene was
- Synthesis examples 2 and 3 [Production of Isobutylene Copolymers A-2 and A-3]
- the isobutylene copolymer A-2 and the isobutylene copolymer were used in the same manner as in Synthesis Example 1 except that the charge ratios of styrene, isobutylene and 1,4-bis (1-methoxy-1-methylethyl) benzene were changed.
- Copolymer A-3 styrene-isobutylene-styrene triblock copolymer
- Table 1 The results analyzed in the same manner as in Synthesis Example 1 are shown in Table 1.
- Example 1 [Preparation of resin composition]
- the isobutylene copolymer (A) was A-1
- EVOH (B) was B-1
- the halogen scavenger (C) was C-1.
- A-1 60 parts by mass
- B-1 40 parts by mass
- C-1 (0.25 parts by mass) was added to the resulting mixture, and then melt-kneaded.
- the pellet of the resin composition was obtained by pelletization and drying.
- Table 2 shows the results of evaluating the crosslinkability of the obtained resin composition by the above method. The melt kneading conditions are shown below.
- Examples 2 to 13 A resin composition was prepared in the same manner as in Example 1 except that the types and addition amounts of the isobutylene copolymer (A), EVOH (B) and halogen scavenger (C) were changed as shown in Table 2. evaluated. Moreover, the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- Examples 14-17 When the addition amount of the halogen scavenger (C) was changed as shown in Table 2 and when the isobutylene copolymer (A) and EVOH (B) were melt-kneaded, the carboxylic acid metal salt (D) was further added.
- a resin composition was prepared and evaluated in the same manner as in Example 1 except that D-1, D-2 or D-3 was added in the amounts shown in Table 2, respectively.
- the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- Comparative Example 1 A resin composition was prepared and evaluated in the same manner as in Example 1 except that the halogen scavenger (C) was not added. Moreover, the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- Comparative Examples 2-4 A resin composition was prepared and evaluated in the same manner as in Example 1 except that the addition amounts of the isobutylene copolymer (A), EVOH (B) and halogen scavenger (C) were changed as shown in Table 2. . Moreover, the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- Comparative Example 5 A resin composition was prepared and evaluated in the same manner as in Example 2 except that B-4, which is a low density polyethylene, was used instead of EVOH (B). Moreover, the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- Comparative Example 6 A resin composition was prepared and evaluated in the same manner as in Example 2 except that A-5, which is a styrene-ethylene / butylene-styrene block copolymer, was used instead of the isobutylene copolymer (A). Moreover, the injection piece and the single layer film were produced and evaluated like Example 1 using the obtained resin composition. Each evaluation result is shown in Table 2.
- the film obtained by molding a resin composition (Comparative Example 3) having a mass ratio (B / A) of EVOH (B) to isobutylene copolymer (A) of less than 20/80 has insufficient gas barrier properties. Met.
- the injection piece obtained by molding a resin composition (Comparative Example 4) in which the mass ratio (B / A) of EVOH (B) to isobutylene copolymer (A) exceeds 50/50 is not flexible. It was enough.
- the resin composition using low density polyethylene instead of EVOH (B) had insufficient gas barrier properties.
- the resin composition using the resin containing no chlorine atom (Comparative Example 6)
- the injection piece and the film could not be molded and could not be evaluated.
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Abstract
Description
Na2O・Al2O3・2SiO2・yH2O (II)
(式I及びII中、xは0~5の数、aは0<a≦0.5を満たす数、yは0~6の数を示す。)
カルボン酸:シュウ酸、コハク酸、安息香酸、クエン酸、酢酸、乳酸等
リン酸化合物:リン酸、亜リン酸等の各種の酸やその塩等
ホウ素化合物:ホウ酸類、ホウ酸エステル、ホウ酸塩、水素化ホウ素類等
本発明の成形体は、前記樹脂組成物からなる。
[塩素原子量]
イソブチレン系共重合体(A)を燃焼・吸収装置(三菱アナリテック社製「AQF-2100H」)にて前処理した。得られた処理液をイオンクロマトグラフ(日本ダイオネクス社製「ICS-2000」)にて測定することで塩素原子量を検出した。
A-1~A-3については、合成例1~合成例3において後述する。
A-4:カネカ製「SIBSTAR 062T」、スチレン-イソブチレン-スチレンブロック共重合体
MFR10g/10分(230℃、荷重2160g);スチレン単位からなる重合体ブロックの含有量24質量%、数平均分子量60000;イソブチレン単位からなる重合体ブロックの含有量77質量%;塩素原子含有量0.11質量%
A-5:旭化成製「Taftec H1041」、スチレン-エチレン・ブチレン-スチレンブロック共重合体
MFR5.0g/10分、スチレン単位からなる重合体ブロックの含有量30質量%;ブタジエン単位からなる重合体ブロックの含有量70質量%;塩素原子含有量0.00質量%
測定装置に日本電子社製「JNM-GX-500型」、溶媒にDMSO-d6を用いた1H-NMR測定により求めた。
メルトインデクサ(東洋精機製作所製「A-111A」)を用い、所定の条件下(イソブチレン系共重合体:温度230℃、荷重2160g;EVOH:温度210℃、荷重2160g)、ASTM D1238に記載の方法で、測定試料の流出速度(g/10分)を測定して求めた。
B-1:クラレ製「EVAL F104B」、EVOH
MFR10.0g/10分、エチレン含有量32モル%、ケン化度99.99モル%
B-2:クラレ製「EVAL L104B」、EVOH
MFR8.9g/10分、エチレン含有量27モル%、ケン化度99.99モル%
B-3:クラレ製「EVAL E105B」、EVOH
MFR13.0g/10分、エチレン含有量44モル%、ケン化度100.0モル%
B-4:日本ポリエチレン製「ノバテックLD LJ400」、低密度ポリエチレン
MFR1.5g/10分(190℃、荷重2160g)、密度0.921g/cm3
C-1:協和化学工業製「ZHT-4A」、ハイドロタルサイト
C-2:協和化学工業製「DHT-4A」、ハイドロタルサイト
D-1:酢酸マグネシウム
D-2:ステアリン酸マグネシウム
D-3:酢酸カルシウム
樹脂組成物を75g秤量し、ローラミキサ(株式会社東洋精機製作所製「R100」)に入れて230℃、100rpmで撹拌しトルク変化を経時観察した。トルクが継続的に1N・m以上、上下に変動し始める時間を計測した。
JIS K 6253-3に従い、後述する射出片を2本重ねて厚み8mmとした状態で島津製作所社製デュロメータ硬度計(タイプA)を用い、デュロメータ硬さを測定した。
後述する単層フィルムを20℃/65%RHの条件下で調湿した後、酸素透過速度測定装置(Modern Control社製「OX-Tran2/20」)を用い、20℃/65%RHの条件下でJIS K 7126(等圧法)に記載の方法に準じて酸素透過度(OTR)を測定した。
後述する単層フィルムを用いて、外観を以下のように評価した。
A:膜面が平滑で、ハイドロタルサイト凝集物が殆どない。
B:膜面が部分的に荒れており、ハイドロタルサイト凝集物がわずかにある。
C:膜面が荒れており、ハイドロタルサイト凝集物が多い。
[イソブチレン系共重合体A-1の製造]
窒素で置換した攪拌機付きの反応器中に、塩化メチレン1060質量部とメチルシクロヘキセン920質量部とからなる混合溶媒、並びに四塩化チタン2.7質量部及び1,4-ビス(1-メトキシ-1-メチルエチル)ベンゼン0.91質量部とからなる重合開始剤を仕込み、-65℃に冷却した後に、イソブチレン150質量部を仕込んで4時間重合させた。さらに、-65℃の冷却下でジメチルアセトアミド0.08質量部およびスチレン38質量部を添加し、4時間重合させた。得られた反応混合物をメタノールで沈殿させて、イソブチレン系共重合体B-1(スチレン-イソブチレン-スチレントリブロック共重合体)を製造した。得られたB-1の数平均分子量はGPC(ゲルパーミエーションクロマトグラフィー)により求め、ブロック共重合体中の各ブロックの数平均分子量は該ブロック共重合体の合成中間体であるポリイソブチレンのGPCに基づいて求め、ブロック共重合体中のスチレン単位からなる重合体ブロックの含有量は1H-NMRにより求めた。これらの分析結果を表1に示す。
[イソブチレン系共重合体A-2、A-3の製造]
スチレン、イソブチレンおよび1,4-ビス(1-メトキシ-1-メチルエチル)ベンゼンの仕込み割合を変更した以外は合成例1と同様の方法を用いて、イソブチレン系共重合体A-2およびイソブチレン系共重合体A-3(スチレン-イソブチレン-スチレントリブロック共重合体)をそれぞれ製造した。合成例1と同様に分析した結果を表1に示す。
[樹脂組成物の作製]
イソブチレン系共重合体(A)としてA-1、EVOH(B)としてB-1、ハロゲン捕捉剤(C)としてC-1をそれぞれ用いた。まず、A-1(60質量部)とB-1(40質量部)とをドライブレンドし、得られた混合物にC-1(0.25質量部)を添加してから溶融混練した後、ペレット化及び乾燥して樹脂組成物のペレットを得た。得られた樹脂組成物の架橋性の評価を上記方法により行った結果を表2に示す。また、溶融混練条件を以下に示す。
<溶融混練条件>
装置:26mmφ二軸押出機(東洋精機製作所製「ラボプラストミル4C150」)
スクリュー:同方向完全噛合型
ダイスホール数:2ホール(3mmφ)
押出温度:C1=200℃、C2からC5=230℃、ダイ=230℃
乾燥:熱風乾燥80℃/6hr
得られた樹脂組成物を以下の条件で射出成形して射出片を作製した。当該射出片のデュロメータ硬さを上記方法により評価した結果を表2に示す。
<射出条件>
装置:射出成形機(日精樹脂工業社製「FS-80S 12AS」)
シリンダー温度:後部/中部/前部/ノズル=200℃/220℃/220℃/200℃
金型温度:60℃
金型:80mm×10mm×4mm×4本
得られた樹脂組成物を以下の条件で製膜し、厚み100μmの単層フィルムを得た。当該単層フィルムの酸素透過度、ハイドロタルサイト凝集物を上記方法により評価した結果を表2に示す。また、製膜条件を以下に示す。
<製膜条件>
装置:20mmφ単軸押出機(東洋精機製作所製「ラボプラストミル4M150」)
L/D:20
スクリュー:フルフライト
ダイ:300mmコートハンガーダイ
押出温度:C1=180℃、C2からC3=220℃、ダイ=220℃
スクリーン:50/100/50
冷却ロール温度:40℃
イソブチレン系共重合体(A)、EVOH(B)及びハロゲン捕捉剤(C)の種類や添加量を表2に示すとおりに変更したこと以外は実施例1と同様にして樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
ハロゲン捕捉剤(C)の添加量を表2に示すとおりに変更したこと、及びイソブチレン系共重合体(A)とEVOH(B)を溶融混練する際に、さらにカルボン酸金属塩(D)としてD-1、D-2又はD-3を表2に示す量をそれぞれ添加したこと以外は実施例1と同様にして、樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
ハロゲン捕捉剤(C)を添加しなかったこと以外は実施例1と同様にして樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
イソブチレン系共重合体(A)、EVOH(B)及びハロゲン捕捉剤(C)の添加量を表2に示すとおりに変更したこと以外は実施例1と同様にして樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
EVOH(B)の代わりに低密度ポリエチレンであるB-4を用いたこと以外は実施例2と同様にして樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
イソブチレン系共重合体(A)の代わりにスチレン-エチレン・ブチレン-スチレンブロック共重合体であるA-5を用いたこと以外は実施例2と同様にして樹脂組成物を作製及び評価した。また、得られた樹脂組成物を用いて実施例1と同様にして射出片及び単層フィルムを作製、評価した。各評価結果を表2に示す。
Claims (11)
- ハロゲン原子を含有するイソブチレン系共重合体(A)、エチレン-ビニルアルコール共重合体(B)及びハロゲン捕捉剤(C)を含有し、
ハロゲン原子を含有するイソブチレン系共重合体(A)に対するエチレン-ビニルアルコール共重合体(B)の質量比(B/A)が20/80~50/50であり、
イソブチレン系共重合体(A)及びエチレン-ビニルアルコール共重合体(B)の総量100質量部に対して、ハロゲン捕捉剤(C)を0.01~1質量部含有する、樹脂組成物。 - ハロゲン捕捉剤(C)が交換性イオンを有する層状無機化合物である、請求項1に記載の樹脂組成物。
- 前記層状無機化合物がハイドロタルサイトである、請求項2に記載の樹脂組成物。
- イソブチレン系共重合体(A)に含有されるハロゲン原子が塩素原子である、請求項1~3のいずれかに記載の樹脂組成物。
- イソブチレン系共重合体(A)が、ビニル芳香族モノマー単位からなる重合体ブロック(a1)と、イソブチレン単位からなる重合体ブロック(a2)とを有するブロック共重合体である、請求項1~4のいずれかに記載の樹脂組成物。
- イソブチレン系共重合体(A)とエチレン-ビニルアルコール共重合体(B)の総量100質量部に対し、カルボン酸金属塩(D)を0.001~0.3質量部含む、請求項1~5のいずれかに記載の樹脂組成物。
- 請求項1~6のいずれかに記載の樹脂組成物からなる層を有する成形体。
- 食品パッケージである請求項7に記載の成形体。
- 容器用パッキンである請求項7に記載の成形体。
- 医療用輸液バッグである請求項7に記載の成形体。
- タイヤ用チューブである請求項7に記載の成形体。
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EP16862163.9A EP3372641B1 (en) | 2015-11-04 | 2016-11-02 | Resin composition containing isobutylene-based copolymer, and molded object |
US15/773,242 US10633532B2 (en) | 2015-11-04 | 2016-11-02 | Resin composition containing isobutylene-based copolymer, and molded object |
CN201680077822.7A CN108431124B (zh) | 2015-11-04 | 2016-11-02 | 包含异丁烯系共聚物的树脂组合物和成形体 |
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US (1) | US10633532B2 (ja) |
EP (1) | EP3372641B1 (ja) |
JP (1) | JP6796077B2 (ja) |
CN (1) | CN108431124B (ja) |
WO (1) | WO2017078103A1 (ja) |
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- 2016-11-02 WO PCT/JP2016/082682 patent/WO2017078103A1/ja active Application Filing
- 2016-11-02 EP EP16862163.9A patent/EP3372641B1/en active Active
- 2016-11-02 JP JP2017548831A patent/JP6796077B2/ja active Active
- 2016-11-02 CN CN201680077822.7A patent/CN108431124B/zh active Active
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Also Published As
Publication number | Publication date |
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JPWO2017078103A1 (ja) | 2018-09-06 |
EP3372641A1 (en) | 2018-09-12 |
CN108431124B (zh) | 2020-10-23 |
US10633532B2 (en) | 2020-04-28 |
JP6796077B2 (ja) | 2020-12-02 |
EP3372641B1 (en) | 2021-05-12 |
US20180319972A1 (en) | 2018-11-08 |
EP3372641A4 (en) | 2019-07-10 |
CN108431124A (zh) | 2018-08-21 |
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