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WO2006098142A1 - Composition pour joint de capsule - Google Patents

Composition pour joint de capsule Download PDF

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Publication number
WO2006098142A1
WO2006098142A1 PCT/JP2006/303655 JP2006303655W WO2006098142A1 WO 2006098142 A1 WO2006098142 A1 WO 2006098142A1 JP 2006303655 W JP2006303655 W JP 2006303655W WO 2006098142 A1 WO2006098142 A1 WO 2006098142A1
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WO
WIPO (PCT)
Prior art keywords
component
weight
cap liner
composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/303655
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English (en)
Japanese (ja)
Inventor
Katsuhiko Kimura
Hironari Nakabayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
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Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Priority to JP2007508055A priority Critical patent/JPWO2006098142A1/ja
Publication of WO2006098142A1 publication Critical patent/WO2006098142A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D53/00—Sealing or packing elements; Sealings formed by liquid or plastics material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08L23/06—Polyethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to a cap liner composition used for a sealing material for beverage caps, which is excellent in sealing properties, gas barrier properties, hygiene, and easy to open in actual use, and , And a cap liner using the same.
  • the cross-linked isobutylene polymer has excellent flexibility, resilience, and gas barrier properties, so that it does not only have a good hermetic sealing property, but also has an oxygen content due to the permeation of oxygen into soft drinks and other contents. Gas content such as carbonated beverages with high internal pressure is unlikely to escape, abnormal opening of the opening torque is prevented, easy opening during actual use, and elution from the liner material is prevented.
  • the present invention relates to a composition for a cap liner used for a sealing material for a beverage cap having excellent hygiene, and a cap liner using the same.
  • liner materials such as cork, soft PVC, polyolefin resin such as low density polyethylene, and styrene elastomer are used as liner materials for container lids such as glass bottles, metal bottles, and PET containers. It was. Of these, cork has excellent impact resilience, but is a natural material and has problems such as quality, supply stability, and dust generation. Although PVC-based materials are flexible and have excellent sealing properties, there are problems such as elution of plasticizers and generation of dioxin during low-temperature incineration. Under these circumstances, in recent years, it has been changed to a liner material such as an olefin resin having excellent hygiene and workability, such as styrene elastomer.
  • a liner material mainly composed of such a styrene elastomer is hydrogenated. It is general to use a composition having a softening power such as styrene-butadiene block copolymer, polyolefin and liquid paraffin (Patent Documents 1 to 4). By using such a composition, it is flexible and has excellent hermetic sealing properties, can withstand hot filling (hot fill) of the contents and heat sterilization (retort sterilization) after filling and sealing, and thermal deformation. In addition, a liner material has been obtained in which leakage due to heat contraction is effectively eliminated.
  • a composition having a softening power such as styrene-butadiene block copolymer, polyolefin and liquid paraffin
  • hydrogenated styrene-butadiene block copolymers have a lower gas permeation rate and a higher ability to block external force oxygen than polyolefins, which may cause acid content.
  • the period in which the flavor and aroma can be maintained immediately is short.
  • the content is a carbonated beverage
  • the period during which the internal pressure can be maintained is short because the carbon dioxide escapes quickly.
  • Patent Document 1 Japanese Patent Laid-Open No. 2-57569
  • Patent Document 2 JP-A-7-76360
  • Patent Document 3 Japanese Patent Laid-Open No. 11-106565
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-38495
  • Patent Document 5 JP 2002-160759 A
  • An object of the present invention is to provide a composition for a cap liner used for a sealing material for a beverage cap, which is excellent in sealing properties, gas noria properties, is excellent in hygiene, and can be easily opened in practical use, and The object is to provide a cap liner using the same.
  • (A) 100 parts by weight of an isobutylene polymer having an alkenyl group at the terminal is melted with (C) a hydrosilyl group-containing compound in the presence of (B) polyolefin 10 to: LOO parts by weight.
  • the present invention relates to a cap liner composition comprising a composition formed by crosslinking during kneading and (D) 0.1 to 20 parts by weight of a lubricant.
  • the present invention relates to a composition for a cap liner comprising -300 parts by weight.
  • a preferred embodiment further relates to a cap liner composition
  • a cap liner composition comprising (F) a softener 1 to LOO parts by weight.
  • the amount of hydrosilyl group in component (C) relative to the alkenyl group in component (A) (hydrosilyl group Zalkyl group) is in the range of 0.5 to 10 in molar ratio. It is related with the composition for cap liners characterized by these.
  • a preferred embodiment relates to a composition for a cap liner, which is at least one selected from the components of component (B) such as polyolefin ink, polyethylene, and polypropylene.
  • the present invention relates to a cap liner composition characterized in that it is at least one selected from the group power consisting of silicone oil.
  • an embodiment relates to a composition for a cap liner, wherein the content of the block (a) in the block copolymer of the component (E) is 10 to 40% by weight.
  • a preferred embodiment relates to a composition for a cap liner, wherein the softening agent of component (F) is polybutene.
  • the present invention also relates to a cap liner having the compositional strength.
  • the cap liner according to the composition of the present invention has an excellent isobutylene polymer. Because of its flexibility and gas noliativity, it is not only good in shape tracking when sealed, but also from the contents of oxygenated drinks such as soft drinks and carbonated drinks with internal pressure. Outgassing is difficult to occur. In addition, the addition of a lubricant prevents an abnormal increase in the opening torque and allows easy opening during actual use. Furthermore, since an alkenyl group is present at the terminal, crosslinking with a hydrosilyl group-containing compound is possible, so that elution of the components of the liner material is prevented. As a result, a cap liner excellent in hygiene can be obtained. Therefore, it is suitable as a cap liner for soft drinks, carbonated drinks, milk drinks and the like.
  • the cap liner composition of the present invention comprises (A) 100 parts by weight of an isoprene-based polymer having an alkenyl group at the terminal, (B) in the presence of 10 to 100 parts by weight of polyolefin, It is obtained by mixing a composition formed by crosslinking during melt-kneading with a drosilyl group-containing compound and (D) 0.1 to 20 parts by weight of a lubricant.
  • the isobutylene-based polymer having an alkenyl group at the terminal which is the component (A) of the present invention, has a unit derived from isoptylene in an amount of 50% by weight or more in terms of flexibility, restorability, and gas noriability. More preferred is 70% by weight or more, and more preferred is 90% by weight or more.
  • the monomer other than isopylene is not particularly limited as long as it is a monomer component that can be cationically polymerized. However, aromatic vinyls, aliphatic olefins, gens such as isoprene, butadiene, dibutenebenzene, and butyl ether. And monomers such as 13 pinene. These may be used alone or in combination of two or more.
  • the molecular weight of the component (A) is not particularly limited, but the weight average molecular weight by GPC measurement is preferably 5,000 to 500,000 ⁇ , 10,000 to 200,000 force ⁇ Especially preferred!
  • the weight average molecular weight is less than 5,000, mechanical properties and the like tend not to be sufficiently exhibited.
  • the weight average molecular weight exceeds 500,000, the melt-kneading property is lowered and the reactivity at the time of crosslinking is reduced. There is a tendency to decrease.
  • the alkenyl group in component (A) of the present invention is particularly limited as long as it is a group containing a carbon-carbon double bond that is active with respect to a crosslinking reaction by a hydrosilyl group-containing compound. is not. Specific examples include a butyl group, a aryl group, a methyl vinyl group, a probe group, a butenyl group, a pentenyl group, a hexenyl group and other aliphatic unsaturated hydrocarbon groups, a cyclopropyl group, a cyclobutyr group, Examples thereof include cyclic unsaturated hydrocarbon groups such as a cyclopentyl group and a cyclohexyl group.
  • a method for introducing an alkenyl group into the terminal of the component (A) of the present invention there is a method such as a hydroxyl group as disclosed in JP-A-3-152164 or JP-A-7-304909. Examples thereof include a method in which a compound having an unsaturated group is reacted with a polymer having a functional group to introduce the unsaturated group into the polymer.
  • a method of performing a Friedel-Crafts reaction with a alkaryl ether, or a method of performing a substitution reaction with allyltrimethylsilane in the presence of lauric acid in order to introduce an unsaturated group into a polymer having a halogen atom.
  • the amount of the alkenyl group of the component (A) of the present invention can be arbitrarily selected according to the required properties. From the viewpoint of the properties after crosslinking, at least 0.2 alkenyl groups per molecule.
  • the polymer having a terminal group is preferably 1.0 or more per molecule, and more preferably 1.5 or more per molecule. If the number is less than 2, the crosslinking reaction may not proceed sufficiently.
  • the polyolefin which is the component (B) of the present invention is a homopolymer of a-olefin, a random copolymer, a block copolymer and a mixture thereof, or ⁇ -olefin and other unsaturated monomers.
  • These random copolymers, block copolymers, graft copolymers and those obtained by oxidation, halogenation or sulfonation of these polymers can be used alone or in combination.
  • polyethylene ethylene-propylene copolymer, ethylene-propylene non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene otaten copolymer, ethylene acetate butyl copolymer, ethylene butyl Alcohol copolymer, ethylene ethyl acrylate copolymer, ethylene acrylic acid copolymer, ethylene methyl acrylate-maleic anhydride copolymer, polyethylene resin such as chlorinated polyethylene, polypropylene, propylene ethylene Random copolymer, propylene ethylene block copolymer, polypropylene resin such as chlorinated polypropylene, poly-1-butene, polyisobutylene, polymethylpentene
  • Examples thereof include (co) polymers of cyclic olefins.
  • polyethylene, polypropylene, or a mixture thereof can be preferably used from the viewpoint of balance between cost and physical properties.
  • Examples of the polyethylene include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • Examples of the polypropylene include homopolypropylene, random polypropylene, and block polypropylene. Among these, polypropylene is most preferable from the viewpoint of heat resistance.
  • the melt flow rate (MFR) of the polyolefin used is not particularly limited, but is preferably 0.1 to LOO (gZlOmin) from the viewpoint of molding fluidity. g ZlOmin) is more preferable.
  • the component (B) not only functions as a crosslinking reaction field for the component (A), but imparts molding fluidity, heat resistance, mechanical strength, and unsealing properties to the final liner composition.
  • the amount of component (B) added is preferably 10 to: LOO parts by weight and 20 to 80 parts by weight per 100 parts by weight of component (A).
  • the amount of the component (B) is less than 10 parts by weight, sufficient molding fluidity tends not to be obtained.
  • the amount is more than 100 parts by weight, flexibility tends to be impaired and sufficient sealing performance tends not to be exhibited.
  • the hydrosilyl group-containing compound (C) is used as the crosslinking agent for the component (A).
  • the hydrosilyl group-containing compound there are no particular restrictions on the hydrosilyl group-containing compound that can be used, but various types of hydrosilyl group-containing polysiloxanes are preferred. Among them, a hydrosilyl group-containing polysiloxane having 3 or more hydrosilyl groups and 3 or more and 500 or less siloxane units is preferable, and a polysiloxane having 3 or more hydrosilyl groups and 10 or more and 200 or less siloxane units. Polysiloxane having 3 or more hydrosilyl groups and 20 to 100 siloxane units is more preferable.
  • the polysiloxane unit here refers to the following general formulas (1), (11), and (III).
  • hydrosilyl group-containing polysiloxane a linear polysiloxane represented by the general formula (IV) or (V);
  • R 1 and R 2 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 3 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group.
  • B represents 3 ⁇ b, a , b, c «3 ⁇ a + b + c ⁇ 500 represents an integer satisfying 00)
  • R 4 and R 5 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 6 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group.
  • E is 3 ⁇ e, d, e, and f are integers satisfying d + e + f ⁇ 500).
  • the component (A) and the hydrosilyl group-containing compound can be mixed at an arbitrary ratio.
  • the amount of hydrosilyl group relative to the alkell group is preferably in the range of 0.5 to 10 in terms of molar ratio, and more preferably 1 to 5.
  • the molar ratio is less than 0.5, crosslinking tends to be insufficient, and when it is more than 10, a large amount of active hydrosilyl groups remain even after crosslinking, and volatile matter tends to be generated. .
  • the crosslinking reaction between the component (A) and the component (C) is preferably performed by adding a hydrosilylated soot catalyst in order to advance the force reaction that proceeds by mixing and heating the two components more quickly.
  • a hydrosilylation catalyst is not particularly limited, and examples thereof include radical generators such as organic peroxides and azo compounds, and transition metal catalysts.
  • the radical generator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy).
  • the transition metal catalyst is not particularly limited.
  • a platinum solid, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include complexes with ketones, platinum-olefin complexes, and platinum (0) -dialkyltetramethyldisiloxane complexes.
  • catalysts other than platinum compounds include RhCl (PPh), RhCl, RuCl, IrCl, FeCl, A1C1, PdCl ⁇ 1 O, NiCl
  • platinum vinylsiloxane is most preferred in terms of crosslinking efficiency.
  • the amount of catalyst is not particularly limited, but is 10 to 1 to 1 mol of alkenyl group (A).
  • 10 _8 mol goodness employed in the range of instrument and it is preferably employed in the range of 10 one 3 ⁇ 10 _6 mol. If the amount is less than 10 _8 moU, the crosslinking tends to be insufficient, and if the amount is more than 10 _ 1 moU, the crosslinking reaction, which is exothermic, tends to be insufficiently controlled.
  • the component (A) is dynamically mixed with the component (C) during melt kneading in the presence of the component (B).
  • Crosslink to The melt kneading temperature is preferably 130 to 240 ° C.
  • the component (B) is not sufficiently melted and the kneading tends to be uneven.
  • component (A) tends to thermally decompose.
  • component (A) and component (B) are essential, but other components such as component (D), component (E), and component (F) are added as appropriate.
  • the force may be cross-linked.
  • the component (D) inhibits the bridge reaction, it is preferable to add the component (D) after crosslinking. Further, when the crosslinking catalyst is added after being mixed with the component (F), the mixture is uniformly diffused and mixed, and the uniformity of the crosslinking reaction tends to be improved. Therefore, such a method is preferably used. In order to promote the mixing of the component (A) and the component (B) and promote the uniform progress of the cross-linking reaction, it is preferable to add the total amount or a part of the blended amount before the cross-linking. . As a method for melt-kneading, a known method without particular limitation can be applied.
  • the component (A) and the component (B), and other components blended in order to obtain predetermined physical properties are heated and kneaded, such as a single screw extruder, twin screw extruder, roll, Banbury mixer, It can be produced by melt-kneading using a Brabender, kneader, high shear mixer or the like.
  • the order of addition is as follows. After component (B) is melted, component (A) is added, and if necessary, other components are added and mixed uniformly, and then a crosslinking agent and a crosslinking catalyst are added. The method of adding and advancing a crosslinking reaction is preferable.
  • the lubricant which is the component (D) of the present invention is added mainly for the purpose of imparting unsealing property (opening property) and moldability.
  • lubricant fatty acid amide lubricants, fatty acid metal salt lubricants, fatty acid ester lubricants, fatty acid lubricants, aliphatic alcohol lubricants, partial esters of fatty acids and polyhydric alcohols, paraffin lubricants, silicone lubricants and the like are preferable. Two or more of these may be selected and used.
  • Fatty acid amide lubricants include: L-force amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylene bis-stearic acid amide, ethylene bis-oleic acid amide, ethylene bis-strong acid amide, ethylene bis-lauric acid Amides, m-xylylene bis stearic acid amides, p-phenylene bis stearic acid amides, and the like.
  • the fatty acid metal salt lubricant include calcium stearate, magnesium stearate, aluminum stearate, zinc stearate, and norium stearate.
  • Fatty acid ester lubricants include methyl laurate, myris Methyl titanate, methyl palmitate, methyl stearate, methyl oleate, methyl oleate, methyl behenate, butyl laurate, butyl stearate, isopyl myristate, isopropyl palmitate, octyl palmitate, Examples include coconut fatty acid octyl ester, octyl stearate, special beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, beef tallow hardened oil, castor hardened oil, and the like.
  • fatty acid-based lubricants include stearic acid, palmitic acid, oleic acid, linoleic acid, and linolenic acid.
  • aliphatic alcohols include stearyl alcohol, cetyl alcohol, myristyl alcohol, and lauryl alcohol.
  • the partial ester of fatty acid and polyhydric alcohol include stearic acid monoglyceride, stearic acid diglyceride, and olein-based monodalyride.
  • paraffinic lubricant include paraffin wax, liquid paraffin, polyethylene wax, oxidized polyethylene wax, and polypropylene wax.
  • montanic acid and its derivatives such as montanic acid ester, montanic acid metal salt, montanic acid partial quinoyl ester, and silicone oil are also used. These may be used alone or in combination.
  • L-acid amide is the most preferable among fatty acid amides from the viewpoint of the effect of improving the opening and molding processability and the influence on the flavor and aroma of the contents.
  • a paraffin wax such as paraffin wax, polyethylene wax, or polypropylene wax
  • silicone oil in combination, the opening performance can be further improved.
  • Silicone oil may be used in a masterbatch with polyolefin for the purpose of improving its mixing and dispersibility.
  • Silicone Concentrate BY—27 series (manufactured by Toray Dow Cowing Silicone Co., Ltd.), Silicone Master Pellet X—22 series (manufactured by Shin-Etsu Chemical Co., Ltd.), Hexa Silicone ML Series (made by Hexa Chemical Co., Ltd.) And other commercial products.
  • Component (D) is mixed in an amount of 0.1 to 20 parts by weight per 100 parts by weight of component (A).
  • a block copolymer having a polymer block (b) force mainly composed of sobutylene may be added.
  • the polymer block (a) mainly composed of an aromatic vinyl compound preferably has 60% by weight or more of units derived from the aromatic vinyl compound in terms of heat resistance. It is more preferable that the polymer block has a higher force.
  • aromatic bur compounds include styrene, o-, m- or p-methylstyrene, ⁇ -methylstyrene, 13-methylolene styrene, 2,6 dimethylstyrene, 2,4 dimethylstyrene, ex-methylolene o-methyl.
  • the polymer block (b) mainly composed of isobutylene is a polymer block in which a unit derived from isobutylene is composed of a force of 60% by weight or more, preferably 80% by weight or more.
  • V and misaligned polymer blocks also use mutual monomers as copolymerization components.
  • other cationically polymerizable monomer components can be used. Examples of such monomer components include aliphatic olefins, gens, and vinyl ethers.
  • Aliphatic olefin monomers include ethylene, propylene, 1-butene, and 2-methyl.
  • Examples include 1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl pentene, butylcyclohexane, otaten, norbornene, and the like.
  • Examples of the gen-based monomer include butadiene, isoprene, hexagen, cyclopentagen, cyclohexagen, dicyclopentagen, divinylbenzene, ethylidene norbornene, and the like.
  • butyl ether monomers include methyl butyl ether, ethyl butyl ether, (n-, iso) propyl butyl ether, (n-, sec-, tert, iso) butyl benzene ether, methyl propylene. And ruether, ethyl propellate and the like.
  • silane compound examples include butyltrichlorosilane, butylmethyldichlorosilane, butyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, dibutyldichlorosilane, divininoresimethoxymethoxysilane, divininoresimethinolesilane, 1,3 dibi- Nole - 1,1,3,3 -tetramethyldisiloxane, trivinylmethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane, and the like.
  • the component (ii) of the present invention is not particularly limited in its structure as long as (a) block and (b) block force are also formed, for example, a linear, branched, star-like structure, etc. Any of a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock copolymer, and the like having bismuth can be selected.
  • a preferable structure includes a triblock copolymer composed of (a)-(b)-(a) from the viewpoint of physical property balance and molding cacheability. These may be used alone or in combination of two or more in order to obtain the desired physical properties and moldability.
  • the ratio of the block (a) to the block (b) is not particularly limited! /, But from the viewpoint of flexibility and rubberity, the content of the block (a) in the component (E) is 5 ⁇ 50% by weight Is more preferably 10 to 40% by weight.
  • the weight average molecular weight by GPC measurement is 30,000 to 500,000. It is preferred to have a power of 50,000 to 300,000, especially preferred!
  • the weight average molecular weight force is lower than 30, 00 0, mechanical properties tend not to be sufficiently developed, whereas when it exceeds 500, 00 00, fluidity and workability tend to be poor. .
  • the method for producing the component (E) is not particularly limited, and can be obtained, for example, by polymerizing the monomer component in the presence of a compound represented by the following general formula (1).
  • X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms or a substituent in which acyloxy group power is also selected
  • R 2 may be the same or different.
  • R 3 is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1-6.
  • the compound represented by the general formula (1) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization.
  • Examples of the compound of the general formula (1) used in the present invention include the following compounds.
  • a Lewis acid catalyst can be allowed to coexist.
  • Such Lewis acids are acceptable as long as they can be used for cationic polymerization.
  • Metal halides such as A1C1 and AlBr; Organometallic halides such as Et A1C1 and EtAlCl
  • TiCl, BC1, and SnCl are preferable in view of the ability as a catalyst and industrial availability.
  • the amount of Lewis acid used is particularly limited.
  • an electron donor component can be further present if necessary.
  • This electron donor component is believed to have the effect of stabilizing the growing carbon cation during cationic polymerization.
  • an electron donor By adding an electron donor, a polymer with a narrow molecular weight distribution and a controlled structure can be obtained. Can be generated.
  • the electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. .
  • the polymerization of the component (E) can be carried out in an organic solvent as necessary.
  • the organic solvent can be used without any particular limitation as long as it does not substantially inhibit force thione polymerization.
  • the amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the polymer solution obtained and ease of heat removal.
  • the respective components are mixed under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C.
  • the temperature range is particularly preferably from 30 ° C to 80 ° C.
  • the component (E) is preferably mixed in an amount of 1 to 300 parts by weight per 100 parts by weight of the component (A), more preferably 1 to 200 parts by weight. If it exceeds 300 parts by weight, the resilience (permanent compression strain) tends to deteriorate.
  • a softening agent can be used as necessary for the purpose of imparting flexibility and molding fluidity.
  • the softening agent is not particularly limited, but generally, a liquid or liquid material is suitably used at room temperature.
  • softeners include mineral oil-based, vegetable oil-based, synthetic-based rubber or rosin softeners.
  • Mineral oils include naphthenic and paraffinic process oils.
  • Vegetable oils include castor oil, cottonseed oil, rapeseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wood
  • the synthetic system include wax, pine oil, olive oil and the like, and polybutene, low molecular weight polybutadiene and the like.
  • polybutene is preferably used from the viewpoints of compatibility with the component (A) and gas noria.
  • Component (F) is blended in an amount of 1 to 100 parts by weight of component (A), preferably 1 to 50 parts by weight of LOO, more preferably 1 to 50 parts by weight. More preferably, it is 30 parts by weight. If it exceeds 100 parts by weight, the softening agent tends to elute into the liner material strength content, which is not preferable.
  • composition for a cap liner of the present invention can be added with an oxygen absorbent for absorbing oxygen in the container and dissolved oxygen in the contents, as well as a force excellent in gas noliativity.
  • an oxygen absorbent known ones can be used, and there is no particular limitation.
  • vitamin C asconolebic acid
  • vitamin E asconolebic acid
  • vitamin E asconolebic acid
  • asconolevate isosconolebic acid
  • isosconolebic acid Salts gallic acid, gallate, propyl gallate, isopropyl citrate, glucose, fructose and other sugars, BHT, BHA, EDTA alkali metal salts
  • tocopherol vitamin E
  • hydroquinone catechol
  • resorcin dibutylhydroxytoluene
  • Organic oxygen absorbers such as bismuth, hydroxybutanol, pyrogallol, longalit, sorbose, glucose, lignin
  • iron oxygen absorbers such as iron powder, activated iron, ferrous oxide, iron salts, sulfites, thiosulfates
  • Inorganic oxygen absorbers such as nitrite, bisulfite, polybutadiene, polyisoprene, or their copolymers,
  • the particle size is not particularly limited, but in general, it is preferably smaller in the sense of increasing the surface area.
  • Oxygen absorbers may contain other substances such as catalysts, water retention agents and hydrates to control their oxygen absorption capacity!
  • an electrolyte can be used in combination with the iron-based oxygen absorbent.
  • the electrolyte is for accelerating the oxygen absorption rate of the iron-based oxygen absorbent, and examples thereof include alkali metal or alkaline earth metal halides, carbonates, sulfates, and hydroxides. Of these, halides are particularly preferred, and CaCl, NaCl, Mg are more preferred.
  • the electrolyte is coated on the iron-based oxygen absorbent particles, or
  • the amount of the electrolyte added is generally about 0.1 to 10% by weight with respect to the iron-based oxygen absorbent.
  • a transition metal catalyst for oxidation reaction can be used in combination with the oxidation-reduction resin used as the polymeric oxygen absorbent.
  • the transition metal catalyst include metal salts such as acetic acid, naphthenic acid, stearic acid, acetylacetonate complex, or molybdenum of hydrochloric acid, iron, conoleto, rhodium, and nickel.
  • a photosensitizer can be used in combination with the redox resin.
  • the photosensitizer that can be used known ones such as a cleavage type and a hydrogen abstraction type can be used, but a hydrogen abstraction type is preferably used. Specifically, those having a benzoin derivative, benzyl ketal, ⁇ -hydroxyacetophenone, and a aminoacetophenone skeleton can be mentioned as the cleavage type.
  • the hydrogen abstraction type photosensitizer include benzophenone, Michler's ketone, anthraquinone, and thixanthone skeleton. These may be used alone or in combination.
  • the cap liner composition of the present invention can also be added with other thermoplastic resins, thermoplastic elastomers, unvulcanized rubber, etc., as long as the performance is not impaired! .
  • Thermoplastic resin includes polystyrene, acrylonitrile monostyrene copolymer, polymethyl methacrylate, polyvinyl chloride, ABS, MBS, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyphenylene ether, polysulfone, polyamide Examples thereof include imide and polyetherimide.
  • thermoplastic elastomer examples include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, nylon elastomers, and the like.
  • unvulcanized rubber examples include butyl rubber, natural rubber, butadiene rubber, isoprene rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), acrylic rubber, and silicone rubber.
  • SBR styrene butadiene rubber
  • NBR acrylonitrile butadiene rubber
  • acrylic rubber examples include silicone rubber.
  • silicone rubber examples include butyl rubber, natural rubber, butadiene rubber, isoprene rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), acrylic rubber, and silicone rubber.
  • polyphenylene ether is preferably used for the purpose of improving
  • Petroleum hydrocarbon resin is a resin having a molecular weight of about 300 to 10000 using petroleum unsaturated hydrocarbon as a direct raw material.
  • Petroleum hydrocarbon resin is a resin having a molecular weight of about 300 to 10000 using petroleum unsaturated hydrocarbon as a direct raw material.
  • aliphatic petroleum resin, alicyclic petroleum resin and its hydrogen Low molecular weight weight of hydrocarbon, aromatic petroleum resin and its hydride, aliphatic aromatic copolymer petroleum resin and its hydride, dicyclopentagen petroleum resin and its hydride, styrene or substituted styrene Combined, coumarone 'indene resin and the like.
  • alicyclic saturated hydrocarbon resin is preferable from the viewpoint of compatibility with the component (A).
  • the cap liner composition of the present invention can be blended with fillers for improving physical properties or for economic merit.
  • suitable fillers include clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, my strength, dullite, aluminum hydroxide, and other kinds of inorganic fillers and various metal powders. Examples thereof include wooden pieces, glass powder, ceramic powder, carbon black, granular or powdered solid fillers such as granular or powdered polymers, and other various natural or artificial short fibers and long fibers.
  • hollow fillers such as inorganic hollow fillers such as glass balloons and silica balloons, polyvinylidene fluoride, and organic hollow fillers that also have polyvinylidene fluoride copolymer power
  • light weight can be achieved.
  • various foaming agents can be mixed to improve various physical properties such as weight reduction and shock absorption, and it is also possible to mix gas mechanically during mixing.
  • talc is preferable from the viewpoint of economy and hygiene.
  • the blending amount of the filler is 1 to 100 parts by weight of component (A): preferably 1 to 50 parts by weight of LOO, more preferably 1 to 30 parts by weight. More preferably, it is part. If it exceeds 100 parts by weight, the flexibility of the resulting composition tends to be impaired, which is not preferable.
  • the cap liner composition of the present invention may be mixed with an antioxidant and an ultraviolet absorber as necessary, and the amount of the mixture is 0 with respect to 100 parts by weight of component (A). It is preferable to be in the range of 01 to 10 parts by weight, and more preferably in the range of 0.01 to 5 parts by weight.
  • flame retardants, antibacterial agents, light stabilizers, colorants, fluidity improvers, antiblocking agents, antistatic agents, etc. can be added as other additives, each of which can be used alone or in combination of two or more. Can be used together.
  • a known method without particular limitation can be applied to the method for producing the composition for a cap liner of the present invention.
  • each of the above-mentioned components and, if necessary, the additive component are heated and kneaded using a single-screw extruder, twin-screw extruder, roll, Banbury mixer, Brabender, kneader, high shear mixer, etc. It can be manufactured by melt-kneading.
  • the kneading order of the components is not particularly limited, and can be determined according to the apparatus used, workability, or physical properties of the obtained cap liner composition.
  • the hardness of the thread liner composite for a cap liner of the present invention is a hardness measured with a spring type A durometer as defined in JIS K-6253 (hereinafter abbreviated as JIS-A hardness). 95 is preferred 50-75 is most preferred.
  • JIS-A hardness is less than 40, the liner material strength is weak and the liner tends to wear when the cap is opened and closed.
  • JIS-A hardness exceeds 90, the liner is too hard and sufficiently adheres to the container mouth. There is a tendency for the hermetic seal contents of the container contents to be damaged.
  • cap liner of the present invention there is no particular limitation.
  • Various types of molding methods and molding apparatuses generally used are used depending on the type, application, and shape of the target cap.
  • any molding method such as injection molding, extrusion molding, press molding, blow molding, calender molding, and casting molding is exemplified, and these methods may be combined.
  • the cap liner composition may be formed into a sheet having a thickness of 0.5 to 1. Omm, then punched out to a diameter suitable for the shape of the cap, and inserted into the cap for adhesion.
  • An in-shell molding method in which a certain amount of extruded molten resin is dropped inside the cap and is embossed under cooling to form a liner.
  • the in-shell mold method is an excellent molding method from the viewpoint of mass productivity.
  • the cap liner composed of the cap liner composition of the present invention may be used as a single layer or in combination with a layer having other functions.
  • the layer having other functions include an oxygen absorption layer.
  • the oxygen absorbing layer is exemplified by a layer in which the above-described oxygen absorber is dispersed in a polymer such as polyolefin.
  • Caps in which the composition for a cap liner of the present invention is used include various types of tea beverages, fruit beverages, vegetable beverages, carbonated beverages, milk beverages, coffee beverages, soft drinks, mineral water PET bottle containers and metals.
  • examples include bottle containers, bottles for beer, whiskey, wine, sake bottles such as sake, wide-mouth bottles for foods such as jam and enokitake, and small bottles for drinks.
  • it is particularly suitable for caps of containers used for PET bottle containers and metal bottle containers.
  • JIS-A hardness the hardness (hereinafter abbreviated as JIS-A hardness) was measured with a spring type A durometer. JIS-A hardness is 50 to 75, ⁇ , 40 to 50 or 75 to 95, ⁇ , less than 40 or more than 95.
  • a 1 mm thick press sheet was used as the test piece.
  • a glass whose contact surface was processed into a spherical surface with a diameter of about 5 mm was used as a sliding piece, a 200 g weight was placed on it, moved at a speed of 3 OmmZ, and the static friction coefficient was measured.
  • the coefficient of static friction is less than 0.5, it is marked as ⁇ , when 0.5 to 1.0 is marked as ⁇ , and when it exceeds 1.0.
  • the oxygen transmission coefficient was measured.
  • a lmm-thick press sheet was used as the test piece, and the differential pressure method (A method) was used.
  • test piece used was a 12. Omm thickness press sheet.
  • a cap liner composition was produced using the following raw materials.
  • Component (A) Isobutylene polymer having an alkenyl group at the terminal
  • High density polyethylene Hi-Zex 2200J manufactured by Mitsui Engineering Co., Ltd. (Density: 0.968 g / cm 3 , MFR: 5.2 gZl0min, hereinafter abbreviated as HDPE)
  • Pt catalyst 1,1,3,3-tetramethyl-1,3-dialkyldisiloxane complex of zerovalent platinum, 3 wt% xylene solution (hereinafter abbreviated as Pt catalyst)
  • Silicone oil Silicone concentrate BY27-001 manufactured by Toray Dow Cowing Silicone Co., Ltd., silicone oil content of about 50% (hereinafter abbreviated as SiMB)
  • Component (E) isobutylene block copolymer
  • Butyl dynamic cross-linking elastomer Trefsin 327 1— 65W308 (hereinafter abbreviated as TREF)
  • a 2 L separable flask was fitted with a three-way cock, thermocouple, and stirring seal, and purged with nitrogen. After nitrogen substitution, nitrogen was flowed using a three-way cock. To this, 785 ml of toluene and 265 ml of ethylcyclohexane were added using a syringe and cooled to about 70 ° C. After cooling, 277 ml (2933 mmol) of isobutylene monomer was added. After cooling to about 70 ° C.
  • the reaction solution was washed twice with water, the solvent was evaporated, and the resulting polymer was vacuum-dried at 60 ° C for 24 hours to obtain the desired block copolymer.
  • the obtained isobutylene block copolymer was subjected to GPC analysis. As a result, the weight average molecular weight was 135,000, and the polystyrene content determined by NMR was 30% by weight.
  • a dynamic crosslinking composition was produced in the same manner as in Production Example 3, except that component (B) was RPP.
  • Laboplast mill (Toyo Seiki Co., Ltd.) was prepared by using the dynamically crosslinked composition produced in Production Examples 3 and 4 and blending so that the final composition of each component was as shown in Table 1. Melt-kneaded for 5 minutes. The charged weight was adjusted to 45 g in total. The obtained kneaded material was press-molded at 170 ° C for 5 minutes, and various physical properties were evaluated. Table 1 shows the evaluation results.
  • melt-kneading was carried out in the same manner as in Production Example 3. However, since the crosslinking did not proceed, the torque did not increase, and only a kneaded product with extremely strong tack was obtained. I got it. Since the force could not be formed into a sheet shape, the physical properties could also be evaluated.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
  • Component (B) HDPE 25 35 45 65 85 65 65 20
  • MFR 0.10 0.10 0.15 0.20 0.20 0.25 0.30 0.25 0.25 0.20 0.20 0.20 0.40
  • Comparative Example 1 is insufficient in the force gas barrier property, which is a composition mainly composed of a hydrogenated styrene monoconjugate block copolymer (SEBS), which is a conventional technique.
  • SEBS hydrogenated styrene monoconjugate block copolymer
  • Comparative Example 2 the force of changing the softening agent to polybutene The stickiness due to the bleeding of the softening agent with poor absorbability to SEBS is strong. Along with this, the gas-opening property is not sufficient.
  • Comparative Example 3 is a composition comprising styrene-isobutylene block copolymer (SIB S) as a main component, but it can be seen that the compression set is high and the restoring property is insufficient.
  • Comparative Example 4 is a commercial product of a composition obtained by dynamically crosslinking butyl rubber, but it can be seen that there is a problem in terms of elution.
  • Example 1 to 9 of the present invention it can be seen that the composition is well balanced as the liner material of the cap without such problems.
  • the resilience tends to decrease as the amount of force added indicating the effect of addition of the isoprene-based block copolymer (SIBS) as the component (E) increases, the gas barrier It can be seen that the moldability and molding fluidity are improved.
  • silicone oil was added as the component (D), and it can be seen that the openability tends to be improved.
  • Example 7 it can be seen that the polyethylene flow is further added as the component (D), and the molding fluidity is improved.
  • Example 8 polypropylene is used as the component (B), and it can be seen that the opening performance is excellent in molding fluidity.
  • the openability after the retort sterilization treatment (121 ° C, 30 minutes) showed a tendency to be superior to that of Example 4 using polyethylene.
  • the cap liner assembly that is the object of the present invention is excellent in hermetic sealability, gas barrier property, restoration property, hygiene, and easy to open during actual use. An adult product is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Closures For Containers (AREA)

Abstract

Composition pour joint de capsule pour utilisation en tant que produit d’étanchéité sur des bouchons de boissons, possédant non seulement d’excellentes propriétés d’étanchéité hermétique (flexibilité et restauration) et de barrière contre les gaz, mais aussi un excellent comportement hygiénique et une facilité d’ouverture à l’usage ; et joint de capsule utilisant cette composition. L’invention concerne une composition pour joint de capsule obtenue par réticulation dynamique d’un polymère d’isobutylène possédant un groupement alcényle à son extrémité, avec l’aide d’un composé contenant des groupements hydrosilyles, en présence d’une polyoléfine, et en ajoutant un lubrifiant.
PCT/JP2006/303655 2005-03-15 2006-02-28 Composition pour joint de capsule Ceased WO2006098142A1 (fr)

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JP2007091770A (ja) * 2005-09-27 2007-04-12 Kaneka Corp キャップライナー用組成物
JP2007119528A (ja) * 2005-10-25 2007-05-17 Kaneka Corp キャップライナー用組成物
WO2009013945A1 (fr) 2007-07-25 2009-01-29 Daikyo Seiko, Ltd. Composé de caoutchouc et article moulé
JP2009249404A (ja) * 2008-04-01 2009-10-29 Toyo Seikan Kaisha Ltd 低温時の耐ストレスクラック性及び滑り性に優れた成形体
JP2010189601A (ja) * 2009-02-20 2010-09-02 Daiwa Can Co Ltd 金属ｐｐキャップ用ライナー樹脂組成物
JP2010536967A (ja) * 2007-08-22 2010-12-02 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 改良した加工性を有する軟質ポリオレフィン組成物
EP2006328A4 (fr) * 2006-04-13 2011-03-02 Kaneka Corp Composition pour bouchons en caoutchouc et bouchons en caoutchouc pour un usage medical
JP2015232095A (ja) * 2014-06-10 2015-12-24 三菱化学株式会社 熱可塑性エラストマー組成物、成形体及びキャップライナー
JP2016150980A (ja) * 2015-02-18 2016-08-22 リケンテクノス株式会社 熱可塑性エラストマー樹脂組成物
JP2016196601A (ja) * 2015-04-06 2016-11-24 リケンテクノス株式会社 熱可塑性エラストマー樹脂組成物
JP2018104572A (ja) * 2016-12-27 2018-07-05 東洋ゴム工業株式会社 動的架橋物、低空気透過性フィルム及び空気入りタイヤ
JP2018123174A (ja) * 2017-01-30 2018-08-09 三井化学株式会社 樹脂組成物およびその成形体

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
JP2007091770A (ja) * 2005-09-27 2007-04-12 Kaneka Corp キャップライナー用組成物
JP2007119528A (ja) * 2005-10-25 2007-05-17 Kaneka Corp キャップライナー用組成物
EP2006328A4 (fr) * 2006-04-13 2011-03-02 Kaneka Corp Composition pour bouchons en caoutchouc et bouchons en caoutchouc pour un usage medical
WO2009013945A1 (fr) 2007-07-25 2009-01-29 Daikyo Seiko, Ltd. Composé de caoutchouc et article moulé
US8101674B2 (en) 2007-07-25 2012-01-24 Daikyo Seiko, Ltd. Rubber compound and molded article
JPWO2009013945A1 (ja) * 2007-07-25 2010-09-30 株式会社大協精工 ゴム配合物および成形品
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JP2010536967A (ja) * 2007-08-22 2010-12-02 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 改良した加工性を有する軟質ポリオレフィン組成物
JP2009249404A (ja) * 2008-04-01 2009-10-29 Toyo Seikan Kaisha Ltd 低温時の耐ストレスクラック性及び滑り性に優れた成形体
JP2010189601A (ja) * 2009-02-20 2010-09-02 Daiwa Can Co Ltd 金属ｐｐキャップ用ライナー樹脂組成物
JP2015232095A (ja) * 2014-06-10 2015-12-24 三菱化学株式会社 熱可塑性エラストマー組成物、成形体及びキャップライナー
JP2016150980A (ja) * 2015-02-18 2016-08-22 リケンテクノス株式会社 熱可塑性エラストマー樹脂組成物
JP2016196601A (ja) * 2015-04-06 2016-11-24 リケンテクノス株式会社 熱可塑性エラストマー樹脂組成物
JP2018104572A (ja) * 2016-12-27 2018-07-05 東洋ゴム工業株式会社 動的架橋物、低空気透過性フィルム及び空気入りタイヤ
JP2018123174A (ja) * 2017-01-30 2018-08-09 三井化学株式会社 樹脂組成物およびその成形体

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