WO2006090722A1 - Ethylene copolymer composition and easily breakable sealing material using same - Google Patents

Ethylene copolymer composition and easily breakable sealing material using same Download PDF

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Publication number
WO2006090722A1
WO2006090722A1 PCT/JP2006/303130 JP2006303130W WO2006090722A1 WO 2006090722 A1 WO2006090722 A1 WO 2006090722A1 JP 2006303130 W JP2006303130 W JP 2006303130W WO 2006090722 A1 WO2006090722 A1 WO 2006090722A1
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Prior art keywords
ethylene
weight
parts
ethylene copolymer
copolymer
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PCT/JP2006/303130
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French (fr)
Japanese (ja)
Inventor
Masanobu Sato
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Du Pont-Mitsui Polychemicals Co., Ltd.
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Application filed by Du Pont-Mitsui Polychemicals Co., Ltd. filed Critical Du Pont-Mitsui Polychemicals Co., Ltd.
Priority to CN2006800054931A priority Critical patent/CN101124279B/en
Priority to JP2007504737A priority patent/JP5188177B2/en
Priority to KR1020077019666A priority patent/KR100909394B1/en
Publication of WO2006090722A1 publication Critical patent/WO2006090722A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • 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

Definitions

  • the present invention relates to an ethylene copolymer composition exhibiting excellent sealing properties and easy-opening properties to various materials, and an easily-openable sealing material comprising the composition. More specifically, the present invention relates to an antifogging ethylene copolymer composition suitable as a sealing material for hydrocarbon polymers such as polypropylene and polystyrene, and an easy-opening sealing material used as the composition.
  • Background art
  • Plastic containers equipped with easily openable lids are widely used as containers for various foods and beverages such as cup cakes, jelly, yogurt, and tofu.
  • Various materials have been proposed and put to practical use as extrusion-laminated seal materials that can be used for the seal layer of such easy-open lids.
  • ethylene 'vinyl acetate copolymer and a tackifier resin composition and a composition in which polyethylene or a low crystalline ethylene' a-olefin copolymer is blended, have sealing properties and easy opening properties. It is known to be a sealing material (see, for example, Patent Documents 1 and 2).
  • the cover material is generally constructed by laminating a sealing material on the entire surface of the base material of the cover material.
  • Patent Document 1 Japanese Patent Publication No. 63-29894
  • Patent Document 2 Japanese Patent Publication No. 1-3895
  • An object of the present invention is to provide an ethylene copolymer composition excellent in sealing properties, low-temperature heat sealing properties, and easy-opening properties against various materials, in particular, hydrocarbon polymers such as polypropylene and polystyrene. There is to do.
  • Another object of the present invention is excellent in sealing properties, low-temperature heat-sealing properties, and easy-opening properties against various materials, especially hydrocarbon polymers such as polypropylene and polystyrene, but exhibiting sufficient antifogging properties. It is desirable to provide an ethylene copolymer composition that serves as a sealing material.
  • Another object of the present invention is to provide an easily openable seal material using such an ethylene copolymer composition and a packaging material obtained by laminating such a seal material on a base material.
  • Ethylene-unsaturated ester copolymer (A) 40 to 98 parts by weight, elastomer (B) 60 to 0 parts by weight and crystalline polyolefin (C) 30 to 0 parts by weight (however, (B) and (C ) Is 2 to 60 parts by weight) and (D) 0-30 parts by weight of a tackifier [where (A), (B), (C), ( The total amount of D) is 100 parts by weight] to provide an ethylene copolymer composition.
  • the present invention also relates to the ethylene 'unsaturated ester copolymer (A) strength, whose unsaturated ester unit content is 3 to 30% by weight, and melting point (T ° C) (JIS K7121
  • ethylene copolymer composition which is an ethylene'unsaturated ester copolymer (A) whose unsaturated ester unit content (X mol%) satisfies the following formula.
  • the above-described ethylene copolymer composition is further blended with up to 10 parts by weight of an antifogging agent (fog) per 100 parts by weight of the polymer component in the ethylene copolymer composition.
  • an antifogging agent Fog
  • An ethylene copolymer composition is provided.
  • the present invention provides an easily openable sealing material such as the ethylene copolymer composition of the present invention.
  • the easy-open sealing material of the present invention can be suitably used for sealing to a hydrocarbon polymer or the like.
  • a packaging material in which the easy-open sealing material is laminated on a base material.
  • heat sealing is performed at a low temperature with moderate heat seal strength and less temperature dependence of heat seal strength with respect to hydrocarbon polymers such as polypropylene and polystyrene. It is possible to provide an easily openable sealing material that can be used.
  • Such an easy-open sealing material can be used as a heat-sealing film for a hydrocarbon-based polymer as a single layer or laminated on a base material. Moreover, it can be laminated on a substrate and used as a cover material for a hydrocarbon polymer container. In particular, when used as a packaging material for foods and drinks, it has excellent anti-fogging properties. Therefore, even if it is stored in a refrigerator, it does not spoil the product image.
  • the present invention relates to an ethylene.unsaturated ester copolymer ( ⁇ ) 40 to 95 parts by weight, an elastomer ( B) 60 to 5 parts by weight and crystalline polyolefin (C) 30 to 0 parts by weight of polymer component 100 parts by weight with respect to 100 parts by weight of antifogging agent (D) at a ratio of 0.01 to: LO parts by weight
  • ⁇ ethylene.unsaturated ester copolymer
  • ⁇ ethylene.unsaturated ester copolymer
  • B elastomer
  • C crystalline polyolefin
  • D antifogging agent
  • Ethylene 'unsaturated ester copolymer (A) is an unsaturated ester unit considering the sealing strength and stickiness to hydrocarbon polymers, or oil resistance in food packaging applications. content from 3 to 30 weight 0/0, and the are suitable particularly range of 4 to 25 wt%.
  • the unsaturated ester of the ethylene / unsaturated ester copolymer (A) is a butyl ester such as butyl acetate or butyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, or acrylic acid.
  • Examples include unsaturated carboxylic acid esters such as isobutyl, n-butyl acrylate, methyl methacrylate, ethyl acetate, isobutyl methacrylate, dimethyl maleate, and jetyl maleate.
  • Particularly preferred unsaturated esters are butyl acetate and lower alkyl esters of acrylic acid or methacrylic acid.
  • Two or more ethylene / unsaturated ester copolymers (A) can be used in combination.
  • Ethylene 'unsaturated ester copolymer (A) is 190 when considering processability, seal strength, oil resistance and the like.
  • C Menore flow rate at 2160g load (JIS K7210-1999) Force ⁇ 0. L-500g / 10min, especially 0.5-150g / 10min.
  • the ethylene / unsaturated ester copolymer (A) as described above can be obtained by radical copolymerization under high temperature and high pressure.
  • a copolymer (A) with good randomness produced by a high-pressure radical polymerization process by a normal autoclave method can be used, but the content of the same unsaturated ester unit with higher heterogeneity than this can be used.
  • the elastomer (B) blended with the ethylene 'unsaturated ester copolymer (A) may be an amorphous or low crystalline olefin copolymer or a styrene thermoplastic elastomer. It can be illustrated.
  • the amorphous or low crystalline olefin copolymer is composed of 2 or more of a0-olefin having 2 to L carbon atoms, and the crystallinity measured by X-ray diffraction method is 40% or less. (0-40%), preferably 7-30% It is a polymer and has rubber-like properties.
  • Typical examples of the copolymer include a copolymer having ethylene or propylene as a main component, and having 2 or more carbon atoms as an auxiliary component, or one or more of ⁇ -olefins other than LO. be able to.
  • the copolymer mainly composed of ethylene, 50 to 90 moles of ethylene polymerization units 0/0, preferably 50 to 70 to 85 mole 0/0, other than ethylene ⁇ Orefin polymerized units: LO mol %, preferably 30 to 15 mole 0/0, 2 mol 0/0 hereinafter Gen monomer polymerization unit if necessary, it can preferably be mentioned those containing more than 1 mole%.
  • ethylene copolymers examples include ethylene 'propylene copolymer, ethylene 1-butene copolymer, ethylene 4-methyl-1 pentene copolymer, ethylene 1-hexene copolymer, ethylene 1 Otaten copolymer and the like can be exemplified. Of these, ethylene / propylene copolymer or ethylene / 1 butene copolymer is particularly preferred! /.
  • the copolymer mainly comprising propylene, 70 to 95 mol of propylene polymerization unit 0/0, preferably from 72 to 90 mole 0/0, 5 to 30 polymerized units other than propylene at- Orefuin Examples are those containing mol%, preferably 10 to 28 mol%.
  • propylene-based copolymer examples include propylene'ethylene copolymer and propylene'1-butene copolymer.
  • the melt flow rate measured at 230 ° C and under a load of 2160g in consideration of moldability and miscibility with the copolymer ( ⁇ ) It is preferable to use (A STM D-1238) force of 0.1 to 500 g / 10 min, particularly 0.5 to 150 g / 10 min.
  • the amorphous or low crystalline olefin copolymer is a vanadium-based catalyst composed of a soluble vanadium compound and an organoaluminum halide in the case of a copolymer mainly composed of ethylene.
  • a meta-octacene catalyst composed of a meta-compound compound such as a zirconium compound coordinated with a pentagel group or the like and an organoaluminum oxide compound. It can be produced by polymerization.
  • a transition metal compound component such as a highly active titanium catalyst component or a meta-catacene catalyst component, an organic aluminum component, and an electron donor, a carrier, etc.
  • a transition metal compound component such as a highly active titanium catalyst component or a meta-catacene catalyst component, an organic aluminum component, and an electron donor, a carrier, etc.
  • Existence of regular olefin polymerization catalyst It can be produced by copolymerizing propylene and other OC-olefins.
  • the ethylene 'unsaturated ester copolymer (A) of the present invention has a melting point by DSC (T ° C).
  • a copolymer satisfying the above is preferably used.
  • X is preferably in the range of 0.5 to 12.2.
  • the ethylene 'unsaturated ester copolymer ( ⁇ ) that satisfies this formula is compared with a copolymer with the same unsaturated ester unit content that has higher heterogeneity compared to a copolymer with good randomness. And the melting point is high.
  • Such a copolymer can be produced, for example, by a multistage polymerization by an autoclave method or a tubular method in a high pressure radical polymerization method. As an example of these production methods, the methods introduced in JP-A-62-273214 and Japanese Patent No. 3423308 can be mentioned.
  • a styrenic thermoplastic elastomer can also be used.
  • a styrene-based thermoplastic elastomer a block copolymer of a polymer block (X) mainly composed of a styrene-based monomer and a block ( ⁇ ⁇ ) mainly composed of a conjugated-gene compound and a conjugated gene of the block copolymer are used. Examples include those obtained by hydrogenating polymerized units.
  • styrenic monomer styrene, a-methylol styrene, butyl toluene, t-butyl styrene and the like can be exemplified, and styrene is particularly preferable.
  • conjugated-gen compound butadiene, isoprene, butadiene, isoprene, and the like are particularly preferable, since they are exemplified by butadiene, isoprene, black-opened plane, 2,3-dimethylbutadiene and the like.
  • Examples of the block copolymer of the polymer block (X) mainly composed of a styrene monomer and the polymer block (Y) mainly composed of a conjugated diene compound include (X—Y) or (X—Y). And a linear, branched, and radial block copolymer represented by X (wherein n is an integer of 1 or more).
  • a typical example is a block copolymer of about 10 to 60% by weight of a styrene monomer polymer block and about 90 to 40% by weight of a conjugated polymer block or a hydrogenated carbohydrate thereof.
  • the styrenic thermoplastic elastomer those having as few olefinic double bonds as possible are desirable.
  • the polymer block mainly composed of the styrene monomer and the polymer block mainly composed of a conjugated diene compound are used. It is preferred that 70% or more, preferably 90% or more, of the conjugation polymer units of the block copolymer are hydrogenated. More specifically, in the polymer block mainly composed of conjugated diene compounds, the bull bonds such as 1, 2 or 3, 4 are 10% or more, preferably 20 to 80%, more preferably 30 to 60%.
  • a mold block copolymer is optimal.
  • X is a styrenic polymer block
  • Y ' is a hydrogenated caroconjugated polymer block, that is, an alkylene copolymer block, specifically an ethylene / butene copolymer block or an ethylene' propylene copolymer block.
  • a merged block is a hydrogenated block copolymer having a styrene compound content of hydrogenated block copolymer of 8 to 50% by weight, preferably 10 to 40% by weight, for example, X—Y′—X
  • X is a styrenic polymer block
  • Y ' is a hydrogenated caroconjugated polymer block, that is, an alkylene copolymer block, specifically an
  • Such a block copolymer is a styrene-butadiene-styrene block copolymer, commonly referred to as SBS, or SIS! /, A butadiene polymer block of a styrene-isoprenestyrene block copolymer. Alternatively, it is obtained by hydrogenating an isoprene polymer block, and generally SEBS! / Is called SEPS! /.
  • thermoplastic styrene elastomers use one that has a male flow (ASTM D1238) force of 0.1 to 500 g / 10 min at 200 ° C and 5 kg load, especially about 0.5 to 150 g / 10 min. It is preferable to do this.
  • the crystalline polyolefin (C) that can be used in the ethylene copolymer composition of the present invention is an olefin homopolymer or a copolymer of olefins having a crystallinity of 40% or more in X-rays.
  • Specific examples include polyethylene, polypropylene, poly-1-butene, poly-4-methyl 1-pentene, and the like having various densities.
  • the linear low density polyethylene is ethylene and ⁇ having 3 or more carbon atoms, preferably 3 to 12 carbon atoms.
  • These are single-site catalysts such as a combination catalyst of a meta-octane catalyst component composed of a compound of zirconium having a ligand having a cyclopentadenyl skeleton and an organoaluminum oxide catalyst component.
  • a multisite catalyst such as a combination catalyst of a titanium catalyst component and an organoaluminum compound catalyst component, ethylene and an ⁇ -olefin having 3 or more carbon atoms such as propylene, 1 butene, 1-pentene, 1-hexene, It can be produced by copolymerizing 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and the like.
  • linear low density polyethylene obtained using a single site catalyst is preferred.
  • linear low density polyethylene considering the miscibility with other components and processability, it is 190 ° C, 2160g load Menore-Floret (ASTM D1238) force ⁇ ).
  • L 500g / 10min, In particular, it is preferable to use one having a content of 0.5 to 150 gZlO.
  • Polypropylene suitable as polyolefin (C) is a propylene homopolymer or a copolymer of propylene mainly composed of propylene and other a-olefin, and has a density of 870 to 930 kg / m 3 , in particular. 880-920kg / m 3 is preferred! Also, a melt flow rate at 230 ° C and a load of 2160 g (ASTM D1238) ⁇ ). 1 to 500 gZlO, particularly 0.5 to 150 gZlO.
  • the ⁇ -olefins copolymerized with propylene in the propylene copolymer are those having 2 to 12 carbon atoms, particularly those having 2 to carbon atoms: LO, specifically, ethylene, 1-butene, Examples thereof include one or more of 1-hexene, 1-octene, 1-decene, 1-decene, 4-methyl-1-pentene, and the like.
  • the propylene copolymer may be a random copolymer or a block copolymer. These polypropylenes can be obtained by polymerizing or copolymerizing propylene in the presence of a stereoregular polyolefin polymerization catalyst.
  • the tackifier resin (D) that can be used in the ethylene copolymer composition of the present invention includes an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, and an aromatic hydrocarbon resin.
  • examples include fats, polyethylene pens, rosins, styrenes, coumarone and indene Can do.
  • Examples of aliphatic hydrocarbon resins include 1-butene, isobutene, butadiene, 1,3 pentagen, isoprene and other fractions containing at least one kind of mono- or diolefins having 4 to 5 carbon atoms. Can be mentioned.
  • an alicyclic hydrocarbon resin the gen component in the subent C to C fraction is polymerized after cyclization dimerization.
  • Examples thereof include a resin obtained by polymerizing cyclic monomers such as cyclopentagen, and a resin obtained by hydrogenating an aromatic hydrocarbon resin.
  • an aromatic hydrocarbon resin a fraction containing at least one C to C vinyl aromatic hydrocarbon such as butyltoluene, indene, and ⁇ -methylstyrene is polymerized.
  • Examples of the resin can be obtained by copolymerizing these fractions and the above aliphatic hydrocarbon fractions.
  • polyterpene-based resin include a pinene polymer, j8-pinene polymer, dipentene polymer, terpene'phenol copolymer, ⁇ -vinene'phenol copolymer, and hydrogenated products thereof. Can do.
  • rosins examples include gum rosin, wood rosin, tall oil and other modified rosins, and modified products thereof.
  • modified products include those that have undergone modification such as hydrogenation, disproportionation, dimerization, and esterification. can do.
  • Styrenic hydrocarbon resin has a low molecular weight and is obtained by polymerizing one or more styrene monomers such as high-purity styrene, butyltoluene, ⁇ -methylstyrene, and isopropyltoluene. Mention may be made of oily polymers.
  • the ethylene copolymer composition of the present invention is used as an easily-openable sealing material for packaging foods and drinks, considering the odorlessness, food hygiene, miscibility with other components, etc. It is preferable to use a resin obtained by hydrogenating a hydrocarbon resin such as a terpene resin.
  • the blending ratio of the ethylene / unsaturated ester copolymer (A) in the ethylene copolymer composition of the present invention is 40 to 98 parts by weight, preferably 40 to 95 parts by weight, more preferably 50 to 90 parts by weight.
  • the blending ratio of the elastomer (B) is 60 to 0 parts by weight, preferably 60 to 2 parts by weight, more preferably 50 to 10 parts by weight, and the blending ratio of the crystalline polyolefin (C) is 30 to 0 parts by weight.
  • Parts preferably 30 to 2 parts by weight, more preferably 20 to 5 parts by weight, and the proportion of the tackifier (D) is preferably in the range of 0 to 30 parts by weight, but (B) and ( C) total
  • the amount should be 2-60 parts by weight [however, the total amount of (A), (B), (C), (D) is 100 parts by weight].
  • the ethylene copolymer composition of the present invention further includes up to 10 parts by weight with respect to 100 parts by weight of the total amount of the polymer components (A), (B) and (C) in the ethylene copolymer composition.
  • Preferably, 0.01 to 10 parts by weight of the antifogging agent (E) can be blended.
  • an antifogging agent it has excellent antifogging properties, has moderate heat seal strength against hydrocarbon polymers such as polypropylene and polystyrene, and has little temperature dependence of heat seal strength. It is possible to obtain an ethylene copolymer composition that makes it possible to provide an easy-open sealing material that can be heat-sealed at a low temperature.
  • nonionic, ionic and cationic surfactants can be used.
  • nonionic surfactants particularly esters of polyhydric alcohols, especially polyethylene glycol, glycerin, diglyceride. It is preferable to use a fatty acid ester of a polyhydric alcohol selected from phosphorus and sorbitan. Two or more of these can be used in combination.
  • additives can be optionally blended.
  • Representative examples of such additives include lubricants used for the purpose of improving extrudability, roll release properties, film slip properties and the like, and Z or roll release agents.
  • These include various amides such as ethylenebisoleamide and ethylene bisphenol amide, polyalkylene glycols such as polyethylene glycol and polypropylene darcol, hydrogenated castor oil, silica, talc and other inorganic additives.
  • the blending amount in these compositions is 0 to 3% by weight, preferably about 0.1 to 3% by weight in the case of inorganic additives, and 0 to 1% by weight, preferably 0.01% in other cases. A range of about 1% by weight is appropriate.
  • Examples of other additives that can be optionally blended include tackifier resins, antioxidants, heat stabilizers, light stabilizers, pigments, and dyes.
  • Tackifying resin is useful for fine adjustment of seal strength.
  • examples of tackifier resins include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, oral resins, styrene resins, and coumarones. Inden rosin can be used.
  • aliphatic hydrocarbon resin examples include polymerizing a fraction containing at least one kind of mono- or olefins having 4 to 5 carbon atoms such as 1-butene, isobutene, butadiene, 1,3-pentagen, and isoprene. Mention may be made of the resulting rosin.
  • alicyclic hydrocarbon resin a resin obtained by polymerizing a gen component in a subent C to C fraction after cyclization dimerization and polymerization is used.
  • Examples thereof include a resin obtained by polymerizing a cyclic monomer such as clopentagen, and a resin obtained by hydrogenating an aromatic hydrocarbon resin.
  • ethylene copolymer composition of the present invention components selected from the above (A) to (E) according to the present invention and other additives blended as necessary are mixed simultaneously or sequentially. Can be prepared.
  • a single screw extruder, a twin screw extruder, a Banbury mixer, various types, etc. are used. For example, it is preferable to melt and mix at 130 to 230 ° C., and the mixing order is not particularly limited.
  • the ethylene copolymer composition of the present invention obtained by force has a melt flow rate (JIS K7210-19999) at 190 ° C and a load of 2160 g, considering extrusion processability, seal strength, and the like. It is desirable that it be prepared to be 400 gZlOmin, especially about 1 to 150gZlOmin.
  • the ethylene copolymer composition of the present invention is suitable as an easily openable seal material, particularly as an easily openable seal material for packaging materials, especially as an easily openable seal material for hydrocarbon polymers such as polypropylene and polystyrene. is there.
  • an easy-open seal material it is usually used in a form laminated to various substrates.
  • the base material used for the purpose of making a cover include paper, aluminum, polyester, polyethylene, polypropylene, (high impact) polystyrene, aluminum-deposited polyester, aluminum-deposited polypropylene, and silica-deposited polyester.
  • Such a substrate need not be a single layer, and may be a laminate of two or more layers.
  • the composition is previously formed into a film by a casting method or an inflation method, and bonded to the substrate by a dry lamination method, the composition A method of extrusion-coating a product directly onto a substrate, a method of using polyethylene or the like as an adhesive layer, a method of laminating on a substrate with an adhesive layer through a sand layer, a method of co-extrusion of a substrate and the composition Etc. can be adopted.
  • the laminate obtained by force can be used as various packaging materials.
  • a cover material for various containers especially polypropylene containers and polystyrene containers
  • it is a cover material having excellent antifogging properties, sealing properties, and easy-opening properties.
  • it can be used not only as a container for these hydrocarbon polymers, but also as a cover material for containers made of other materials, for example, containers of polyester, polycarbonate, polysalt gel, etc.
  • Such a container with a lid can be used, for example, for various packaging of foods such as jelly, pudding, yogurt, honey bean, sour, tofu, lactic acid beverage, Japanese confectionery, processed meat, medicines, medical containers, and toner it can.
  • EMA ethylene 'methyl acrylate copolymer (methyl acrylate unit content 20 wt 0/0, melt flow rate (190.C, 2160 g load, JIS K7210- 1999) 8gZlO fraction, mp 9 2 ° C)
  • SEBS Styrene 'ethylene / butene-styrene block copolymer (trade name: Kraton G 1657, styrene polymer block 13 weight 0/0, ethylene Z butene polymer block 87 wt%, melt flow rate (200.C, 5 kg , ASTM D1938) 8g / 10min)
  • mPE 1 Linear low-density polyethylene manufactured with a single-site catalyst (trade name: Evolue SC00100, manufactured by Mitsui Engineering Co., Ltd., density 902kgZm 3 , Mel-Floret (190.C, 2160g Load, ASTM D1238) 8gZlO min)
  • mPE 2 Linear low-density polyethylene produced with a single site catalyst (trade name: Evolue SP0540, manufactured by Mitsui Chemicals, Ltd., density 903kgZm 3 , melt flow rate (190.C, 2 160g load) , ASTM D1238) 3. 8gZlO min)
  • P115 Hydrogenated aromatic hydrocarbon resin (trade name: Archon AMI (Arakawa Chemical Co., Ltd., ring and ball softening point 115 ° C)
  • Diglycerin fatty acid ester (trade name: Riquemar 0— 71— DE, manufactured by Riken Vitamin Co., Ltd.)
  • test substrate was superposed on a 300 ⁇ m-thick polypropylene sheet or polystyrene sheet so that the ethylene copolymer composition surface abuts it, and temperatures of 120 ° C., 140 ° C. and 160 ° C.,
  • the laminate was obtained by heat sealing under the conditions of pressure 0.2 MPa and sealing time 1.0 seconds.
  • the laminate strength was also measured for peel strength when the test substrate was peeled off.
  • Each component was melt kneaded at 150 ° C. using a single-screw extruder at the composition ratio shown in Table 2 to produce a composition.
  • test substrate was placed on a 300 ⁇ m thick polystyrene sheet so that the ethylene copolymer composition surface was in contact with it, and the temperature and pressure were 120 ° C, 140 ° C and 160 ° C.
  • the laminate was obtained by heat sealing under conditions of 0.2 MPa and a sealing time of 1.0 second. The peel strength when the test substrate part was peeled from this laminate was measured.
  • a test substrate was prepared in the same manner as in Example 11 except that the ethylene copolymer composition having the composition shown in Table 3 was used, and its antifogging property was evaluated.
  • a laminate was prepared by heat sealing in the same manner as in Example 11 except that this test substrate was used and a polypropylene sheet was used instead of the polystyrene sheet, and the peel strength was measured in the same manner. The results are also shown in Table 3.
  • the present invention has excellent anti-fogging properties, has an appropriate heat seal strength with respect to hydrocarbon polymers such as polypropylene and polystyrene, has little temperature dependency of the heat seal strength, and has a low temperature.
  • An easily openable sealing material that can be heat-sealed is provided.
  • Such an easy-open sealing material can be used as a heat-sealing film for a hydrocarbon polymer in a single layer or laminated on a base material. Laminate it on the base material, It can be used as a lid material for hydrogenated polymer containers and the like. In particular, when used as a packaging material for foods and drinks, it has excellent anti-fogging properties. Therefore, even if it is stored in a refrigerator, it does not spoil the product image.

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Abstract

Disclosed is an ethylene copolymer composition suitable as a sealing material for hydrocarbon polymers such as polypropylenes and polystyrenes. Also disclosed is an ethylene copolymer composition which forms a sealing material having excellent sealing performance, low-temperature heat sealing performance and seal breakability for hydrocarbon polymers while exhibiting sufficient antifogging properties. Further disclosed is an easily breakable sealing material composed of such a copolymer composition. Specifically disclosed is an ethylene copolymer composition containing 40-98 parts by weight of an ethylene/unsaturated ester copolymer (A), 60-0 parts by weight of an elastomer (B), 30-0 parts by weight of a crystalline polyolefin (C) (the total amount of (B) and (C) is 2-60 parts by weight) and 0-30 parts by weight of a tackifier (D). In a preferable mode of such an ethylene copolymer composition, the content of unsaturated ester unit in the ethylene copolymer (A) is 3-30% by weight, and the melting point (T ˚C) and the content of unsaturated ester unit (X mol%) satisfy the following formula : -3.0X + 125 ≥ T ≥ -3.0X + 109.

Description

明 細 書  Specification
エチレン共重合体組成物及びそれを用いた易開封性シール材料 技術分野  Technical field of ethylene copolymer composition and easy-open sealing material using the same
[0001] 本発明は、種々の材料に対して優れた密封性と易開封性を示すエチレン共重合体 組成物及び該組成物からなる易開封性シール材料に関する。より詳細には、ポリプロ ピレンやポリスチレンなどの炭化水素系重合体のシール材料として好適な、防曇性 エチレン共重合体組成物及び該組成物カゝらなる易開封性シール材料に関する。 背景技術  [0001] The present invention relates to an ethylene copolymer composition exhibiting excellent sealing properties and easy-opening properties to various materials, and an easily-openable sealing material comprising the composition. More specifically, the present invention relates to an antifogging ethylene copolymer composition suitable as a sealing material for hydrocarbon polymers such as polypropylene and polystyrene, and an easy-opening sealing material used as the composition. Background art
[0002] カップ麵、ゼリー、ヨーグルト、豆腐など各種飲食品や医薬品の容器として、易開封 性蓋材を備えたプラスチック容器が広く使用されている。このような易開封性蓋材の シール層に用いられる押出ラミネートカ卩ェ可能なシール材料として種々のものが提 案され、また実用化されてきた。例えばエチレン '酢酸ビニル共重合体と粘着付与榭 脂の組成物、これにポリエチレンや低結晶性エチレン' aーォレフイン共重合体など を配合した組成物などが、密封性と易開封性とを備えたシール材料となることが知ら れて 、る（例えば特許文献 1〜2参照)。  [0002] Plastic containers equipped with easily openable lids are widely used as containers for various foods and beverages such as cup cakes, jelly, yogurt, and tofu. Various materials have been proposed and put to practical use as extrusion-laminated seal materials that can be used for the seal layer of such easy-open lids. For example, ethylene 'vinyl acetate copolymer and a tackifier resin composition, and a composition in which polyethylene or a low crystalline ethylene' a-olefin copolymer is blended, have sealing properties and easy opening properties. It is known to be a sealing material (see, for example, Patent Documents 1 and 2).
[0003] しカゝしながら容器本体に使用されるプラスチック材料の種類も増え、新しい材料に 対しては従来のシール材料では充分に対応できな 、ものもあり、新たなシール材料 の出現が望まれている。また既存のプラスチック材料を使用した容器であっても、用 途によっては望まれるヒートシール特性が異なっていたり、また他の特性が要求され たりすることがあり、このような要求に耐えられるようなシール材料も望まれている。  [0003] However, the types of plastic materials used for the container body are increasing, and some new materials cannot be adequately handled by conventional sealing materials, and new sealing materials are expected to appear. It is rare. Even in containers using existing plastic materials, the desired heat seal characteristics may differ depending on the application, or other characteristics may be required. Seal materials are also desired.
[0004] 例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリエステルなどが容器材料と して古くから使用されてきたが、多くの場合、容器材料に合わせたシール材料が個別 に選択され、使用されていた。ところが近年、コストダウンの要請が強ぐ種々の容器 材料に共通して使用可能なシール材料が望まれている。とくにコスト、その他の特性 力 ポリプロピレンやポリスチレンの容器の使用が増えている力 これに共通して使用 可能な易開封性シール材料が求められて ヽる。  [0004] For example, polyethylene, polypropylene, polystyrene, polyester, and the like have been used as container materials for a long time, but in many cases, a seal material suitable for the container material was individually selected and used. However, in recent years, a seal material that can be used in common for various container materials, for which cost reduction is strongly demanded, has been desired. In particular, cost and other characteristics. Strength The use of polypropylene and polystyrene containers is increasing. There is a need for easy-open seal materials that can be used in common.
[0005] ところでこの種の易開封性シール材料においては、従来、ヒートシール強度を中心 とした評価がなされており、シール層には、直接防曇性が要求されることはないため、 防曇性に着目した検討はなされていな力つた。し力るに蓋材は、一般に、蓋材の基 材全面にシール材料が積層されて構成されており、飲食品等の容器等に使用して冷 蔵庫に保管されると、シール部以外の部分で曇りが生じることがあった。この場合、透 明容器においては内容物が見えに《なり、消費者の印象を悪くするという問題点が めつに。 [0005] By the way, this type of easy-open sealing material has hitherto focused on heat seal strength. Since the seal layer is not required to have antifogging properties directly, it has not been studied focusing on antifogging properties. On the other hand, the cover material is generally constructed by laminating a sealing material on the entire surface of the base material of the cover material. When the cover material is used for containers such as food and drink and stored in a refrigerator, There was a case where fogging occurred in this part. In this case, the contents of the transparent container become visible, and the consumer's impression is worsened.
[0006] そこでシール材料に防曇剤を配合することによってこの問題を解決しょうとする場合 、シール材料によっては防曇効果が認められな 、場合やシール性能に悪影響を及 ぼす場合があり、優れたシール性能と防曇性を併せ持つシール材料の開発は必ず しも容易ではな力つた。  [0006] Therefore, when trying to solve this problem by adding an antifogging agent to the sealing material, the antifogging effect may not be recognized depending on the sealing material, and the sealing performance may be adversely affected. The development of sealing materials that combine excellent sealing performance and anti-fogging properties has not always been easy.
[0007] 特許文献 1：特公昭 63— 29894号公報  [0007] Patent Document 1: Japanese Patent Publication No. 63-29894
特許文献 2：特公平 1― 3895号公報  Patent Document 2: Japanese Patent Publication No. 1-3895
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0008] 本発明の目的は、種々の材料、とりわけポリプロピレンやポリスチレンなどの炭化水 素系重合体に対して密封性、低温ヒートシール性、易開封性に優れたエチレン共重 合体組成物を提供することにある。 [0008] An object of the present invention is to provide an ethylene copolymer composition excellent in sealing properties, low-temperature heat sealing properties, and easy-opening properties against various materials, in particular, hydrocarbon polymers such as polypropylene and polystyrene. There is to do.
また本発明の他の目的は、種々の材料、とりわけポリプロピレンやポリスチレンなど の炭化水素系重合体に対して密封性、低温ヒートシール性、易開封性に優れ、しか も充分な防曇性を示すシール材料となるエチレン共重合体組成物を提供すること〖こ ある。  Another object of the present invention is excellent in sealing properties, low-temperature heat-sealing properties, and easy-opening properties against various materials, especially hydrocarbon polymers such as polypropylene and polystyrene, but exhibiting sufficient antifogging properties. It is desirable to provide an ethylene copolymer composition that serves as a sealing material.
本発明の他の目的は、このようなエチレン共重合体組成物を用いた易開封性シー ル材料、及び基材にこのようなシール材料を積層してなる包装材料を提供することに ある。  Another object of the present invention is to provide an easily openable seal material using such an ethylene copolymer composition and a packaging material obtained by laminating such a seal material on a base material.
課題を解決するための手段  Means for solving the problem
[0009] エチレン.不飽和エステル共重合体 (A) 40〜98重量部、エラストマ一（B) 60〜0 重量部及び結晶性ポリオレフイン (C) 30〜0重量部（ただし (B)と (C)の合計量は 2 〜60重量部である）および (D)粘着付与剤 0〜30重量部 [ただし (A)、 (B)、（C)、（ D)の合計量は 100重量部]からなるエチレン共重合体組成物を提供する。 [0009] Ethylene-unsaturated ester copolymer (A) 40 to 98 parts by weight, elastomer (B) 60 to 0 parts by weight and crystalline polyolefin (C) 30 to 0 parts by weight (however, (B) and (C ) Is 2 to 60 parts by weight) and (D) 0-30 parts by weight of a tackifier [where (A), (B), (C), ( The total amount of D) is 100 parts by weight] to provide an ethylene copolymer composition.
[0010] 本発明はまた、前記エチレン '不飽和エステル共重合体 (A)力 その不飽和エステ ル単位含有量が 3〜30重量％であって、融点（T°C) (JIS K7121〖こ準拠）と不飽和 エステル単位含有量 (Xモル％)が下記式を満足するエチレン '不飽和エステル共重 合体 (A)である前記したエチレン共重合体組成物を提供する。 [0010] The present invention also relates to the ethylene 'unsaturated ester copolymer (A) strength, whose unsaturated ester unit content is 3 to 30% by weight, and melting point (T ° C) (JIS K7121 According to the present invention, there is provided the above-mentioned ethylene copolymer composition which is an ethylene'unsaturated ester copolymer (A) whose unsaturated ester unit content (X mol%) satisfies the following formula.
3. 0X+ 125≥T≥— 3. 0X+ 109  3. 0X + 125≥T≥— 3. 0X + 109
[0011] また本発明は、前記したエチレン共重合体組成物が、さらにエチレン共重合体組 成物中の重合体成分 100重量部に対し 10重量部までの防曇剤 (Ε)を配合したェチ レン共重合体組成物を提供する。 [0011] Further, according to the present invention, the above-described ethylene copolymer composition is further blended with up to 10 parts by weight of an antifogging agent (fog) per 100 parts by weight of the polymer component in the ethylene copolymer composition. An ethylene copolymer composition is provided.
[0012] 本発明は、本発明のエチレン共重合体組成物カゝらなる易開封性シール材料が提 供される。本発明の易開封性シール材料は、炭化水素系重合体などにシールする のに好適に使用することができる。 [0012] The present invention provides an easily openable sealing material such as the ethylene copolymer composition of the present invention. The easy-open sealing material of the present invention can be suitably used for sealing to a hydrocarbon polymer or the like.
本発明によれば、基材に前記易開封性シール材料が積層されてなる包装材料も提 供される。  According to the present invention, there is also provided a packaging material in which the easy-open sealing material is laminated on a base material.
発明の効果  The invention's effect
[0013] 本発明によれば、ポリプロピレンやポリスチレンなどの炭化水素系重合体に対して、 適度なヒートシール強度を有し、ヒートシール強度の温度依存性も少なぐ低温でヒ ートシールすることが可能な易開封性シール材料を提供することができる。  [0013] According to the present invention, it is possible to heat seal at a low temperature with moderate heat seal strength and less temperature dependence of heat seal strength for hydrocarbon polymers such as polypropylene and polystyrene. An easy-open seal material can be provided.
[0014] 本発明によれば、またポリプロピレンやポリスチレンなどの炭化水素系重合体に対 して、適度なヒートシール強度を有し、ヒートシール強度の温度依存性も少なぐ低温 でヒートシールすることが可能な易開封性シール材料を提供することができる。  [0014] According to the present invention, heat sealing is performed at a low temperature with moderate heat seal strength and less temperature dependence of heat seal strength with respect to hydrocarbon polymers such as polypropylene and polystyrene. It is possible to provide an easily openable sealing material that can be used.
[0015] このような易開封性シール材料は、単層であるいは基材に積層して、炭化水素系 重合体に対する熱融着フィルムとして使用することができる。また基材に積層して、炭 化水素系重合体容器などの蓋材として使用することができる。とくに飲食品の包装材 料として使用するときに、防曇性が優れているので、冷蔵庫に保存された場合にも曇 りを生じることはなぐ商品イメージを損なうことはない。  [0015] Such an easy-open sealing material can be used as a heat-sealing film for a hydrocarbon-based polymer as a single layer or laminated on a base material. Moreover, it can be laminated on a substrate and used as a cover material for a hydrocarbon polymer container. In particular, when used as a packaging material for foods and drinks, it has excellent anti-fogging properties. Therefore, even if it is stored in a refrigerator, it does not spoil the product image.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] 本発明は、エチレン.不飽和エステル共重合体 (Α) 40〜95重量部、エラストマ一（ B) 60〜5重量部及び結晶性ポリオレフイン (C) 30〜0重量部からなる重合体成分 1 00重量部に対して、防曇剤（D)を 0. 01〜： LO重量部の割合で配合してなるエチレン 共重合体組成物を提供する。 [0016] The present invention relates to an ethylene.unsaturated ester copolymer (Α) 40 to 95 parts by weight, an elastomer ( B) 60 to 5 parts by weight and crystalline polyolefin (C) 30 to 0 parts by weight of polymer component 100 parts by weight with respect to 100 parts by weight of antifogging agent (D) at a ratio of 0.01 to: LO parts by weight An ethylene copolymer composition is provided.
[0017] エチレン '不飽和エステル共重合体 (A)としては、炭化水素系重合体に対するシー ル強度やべたつきの程度、あるいは食品包装用途においては耐油性などを考慮す ると、不飽和エステル単位含有量が 3〜30重量0 /0、とくに 4〜25重量％の範囲のも のが好適である。エチレン ·不飽和エステル共重合体 (A)の不飽和エステルとしては 、酢酸ビュル、プロピオン酸ビュルのようなビュルエステル、アクリル酸メチル、アタリ ル酸ェチル、アクリル酸イソプロピル、アクリル酸 nプロピル、アクリル酸イソブチル、ァ クリル酸 nブチル、メタクリル酸メチル、メタクリル酸ェチル、メタクリル酸イソブチル、マ レイン酸ジメチル、マレイン酸ジェチルのような不飽和カルボン酸エステルを例示す ることができる。とくに好ましい不飽和エステルは、酢酸ビュル及びアクリル酸又はメタ クリル酸の低級アルキルエステルである。エチレン.不飽和エステル共重合体 (A)は 2種以上混合して使用することができる。 [0017] Ethylene 'unsaturated ester copolymer (A) is an unsaturated ester unit considering the sealing strength and stickiness to hydrocarbon polymers, or oil resistance in food packaging applications. content from 3 to 30 weight 0/0, and the are suitable particularly range of 4 to 25 wt%. The unsaturated ester of the ethylene / unsaturated ester copolymer (A) is a butyl ester such as butyl acetate or butyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, or acrylic acid. Examples include unsaturated carboxylic acid esters such as isobutyl, n-butyl acrylate, methyl methacrylate, ethyl acetate, isobutyl methacrylate, dimethyl maleate, and jetyl maleate. Particularly preferred unsaturated esters are butyl acetate and lower alkyl esters of acrylic acid or methacrylic acid. Two or more ethylene / unsaturated ester copolymers (A) can be used in combination.
[0018] エチレン '不飽和エステル共重合体 (A)はまた、加工性、シール強度、耐油性等を 勘案すると、 190。C、 2160g荷重におけるメノレトフローレート (JIS K7210- 1999) 力 ^0. l〜500g/10分、とくに 0. 5〜150g/10分のものを使用するの力 子まし!/、。  [0018] Ethylene 'unsaturated ester copolymer (A) is 190 when considering processability, seal strength, oil resistance and the like. C, Menore flow rate at 2160g load (JIS K7210-1999) Force ^ 0. L-500g / 10min, especially 0.5-150g / 10min.
[0019] 上記のようなエチレン ·不飽和エステル共重合体 (A)は、高温、高圧下のラジカル 共重合によって得ることができる。例えば通常のオートクレープ法による高圧ラジカル 重合プロセスによって製造されるランダム性良好な共重合体 (A)を使用することがで きるが、これより不均一性が高ぐ同一不飽和エステル単位含有量のもので比較して 融点が高い、チューブラー法による高圧ラジカル重合プロセスによって製造される共 重合体 (A)が特に好適に用いられる。  [0019] The ethylene / unsaturated ester copolymer (A) as described above can be obtained by radical copolymerization under high temperature and high pressure. For example, a copolymer (A) with good randomness produced by a high-pressure radical polymerization process by a normal autoclave method can be used, but the content of the same unsaturated ester unit with higher heterogeneity than this can be used. A copolymer (A) produced by a high-pressure radical polymerization process by a tubular method, which has a higher melting point than that of the polymer, is particularly preferably used.
[0020] 本発明において上記エチレン '不飽和エステル共重合体 (A)に配合されるエラスト マー（B)としては、非晶性又は低結晶性のォレフィン共重合体あるいはスチレン系熱 可塑性エラストマ一を例示することができる。非晶性又は低結晶性のォレフィン共重 合体としては、炭素数が 2〜： L0の aーォレフインの二種以上を構成成分とし、 X線回 折法によって測定される結晶化度が 40%以下 (0〜40%)、好ましくは 7〜30%の共 重合体であって、ゴム的な性質を有するものである。その共重合体の代表例は、ェチ レン又はプロピレンを主成分とし、それらに炭素数 2〜： LOの他の α—ォレフインの 1 種または 2種以上を副成分とする共重合体を挙げることができる。 [0020] In the present invention, the elastomer (B) blended with the ethylene 'unsaturated ester copolymer (A) may be an amorphous or low crystalline olefin copolymer or a styrene thermoplastic elastomer. It can be illustrated. The amorphous or low crystalline olefin copolymer is composed of 2 or more of a0-olefin having 2 to L carbon atoms, and the crystallinity measured by X-ray diffraction method is 40% or less. (0-40%), preferably 7-30% It is a polymer and has rubber-like properties. Typical examples of the copolymer include a copolymer having ethylene or propylene as a main component, and having 2 or more carbon atoms as an auxiliary component, or one or more of α-olefins other than LO. be able to.
[0021] エチレンを主成分とする共重合体としては、エチレン重合単位を 50〜90モル0 /0、 好ましくは 70〜85モル0 /0、エチレン以外の α ォレフィン重合単位を 50〜： LOモル %、好ましくは 30〜15モル0 /0、必要に応じてジェンモノマー重合単位を 2モル0 /0以 下、好ましくは 1モル％以下含有するものを挙げることができる。そのようなエチレン系 共重合体として、エチレン 'プロピレン共重合体、エチレン · 1ーブテン共重合体、ェ チレン · 4ーメチルー 1 ペンテン共重合体、エチレン · 1一へキセン共重合体、ェチ レン · 1 オタテン共重合体等を例示することができる。これらの中ではとくに、ェチレ ン ·プロピレン共重合体又はエチレン · 1 ブテン共重合体が好まし!/、。 [0021] The copolymer mainly composed of ethylene, 50 to 90 moles of ethylene polymerization units 0/0, preferably 50 to 70 to 85 mole 0/0, other than ethylene α Orefin polymerized units: LO mol %, preferably 30 to 15 mole 0/0, 2 mol 0/0 hereinafter Gen monomer polymerization unit if necessary, it can preferably be mentioned those containing more than 1 mole%. Examples of such ethylene copolymers include ethylene 'propylene copolymer, ethylene 1-butene copolymer, ethylene 4-methyl-1 pentene copolymer, ethylene 1-hexene copolymer, ethylene 1 Otaten copolymer and the like can be exemplified. Of these, ethylene / propylene copolymer or ethylene / 1 butene copolymer is particularly preferred! /.
[0022] またプロピレンを主成分とする共重合体は、プロピレン重合単位を 70〜95モル0 /0、 好ましくは 72〜90モル0 /0、プロピレン以外の at—ォレフインの重合単位を 5〜30モ ル％、好ましくは 10〜28モル％含有するものを例示することができる。そのようなプロ ピレン系共重合体としては、プロピレン 'エチレン共重合体およびプロピレン' 1ーブテ ン共重合体を例示することができる。 [0022] The copolymer mainly comprising propylene, 70 to 95 mol of propylene polymerization unit 0/0, preferably from 72 to 90 mole 0/0, 5 to 30 polymerized units other than propylene at- Orefuin Examples are those containing mol%, preferably 10 to 28 mol%. Examples of such a propylene-based copolymer include propylene'ethylene copolymer and propylene'1-butene copolymer.
[0023] 上記非晶性又は低結晶性のォレフィン共重合体としては、成形性、共重合体 (Α)と の混和性などを考慮すると、 230°C、 2160g荷重下で測定したメルトフローレート (A STM D— 1238)力 0. l〜500g/ 10分、とくに 0. 5〜150g/ 10分のものを使 用するのが好ましい。  [0023] As the amorphous or low crystalline olefin copolymer, the melt flow rate measured at 230 ° C and under a load of 2160g in consideration of moldability and miscibility with the copolymer (Α) It is preferable to use (A STM D-1238) force of 0.1 to 500 g / 10 min, particularly 0.5 to 150 g / 10 min.
[0024] 上記非晶性又は低結晶性のォレフィン共重合体は、エチレンを主成分とする共重 合体の場合は、可溶性バナジウム化合物と有機アルミニウムハライドとからなるバナ ジゥム系触媒、ある ヽはシクロペンタジェ -ル基等が配位したジルコニウム化合物等 のメタ口センィ匕合物と有機アルミニウムォキシィ匕合物とからなるメタ口セン系触媒の存 在下に、エチレン及びその他ひーォレフィン類を共重合させることによって製造する ことができる。またプロピレンを主成分とする共重合体の場合は、高活性チタン触媒 成分あるいはメタ口セン系触媒成分などの遷移金属化合物成分、有機アルミニウム 成分、必要に応じて電子供与体、担体等を含む立体規則性ォレフイン重合触媒の存 在下に、プロピレンと他の OCーォレフインを共重合させることによって製造することが できる。 [0024] The amorphous or low crystalline olefin copolymer is a vanadium-based catalyst composed of a soluble vanadium compound and an organoaluminum halide in the case of a copolymer mainly composed of ethylene. Coexisting ethylene and other olefins in the presence of a meta-octacene catalyst composed of a meta-compound compound such as a zirconium compound coordinated with a pentagel group or the like and an organoaluminum oxide compound. It can be produced by polymerization. In the case of a copolymer containing propylene as a main component, a transition metal compound component such as a highly active titanium catalyst component or a meta-catacene catalyst component, an organic aluminum component, and an electron donor, a carrier, etc. Existence of regular olefin polymerization catalyst It can be produced by copolymerizing propylene and other OC-olefins.
[0025] 本発明のエチレン '不飽和エステル共重合体 (A)としては、 DSCによる融点 (T°C)  [0025] The ethylene 'unsaturated ester copolymer (A) of the present invention has a melting point by DSC (T ° C).
(JIS K7121に準拠）が、不飽和エステル単位含有量 (Xモル％)との関係において 、 T 3己  (According to JIS K7121), in relation to the unsaturated ester unit content (X mol%), T 3
3. OX+ 125≥T≥— 3. OX+ 109  3. OX + 125≥T≥— 3. OX + 109
を満足する共重合体が好ましく用いられる。本発明では、 Xは 0. 5〜12. 2の範囲に あることが好ましい。この式を満足するエチレン '不飽和エステル共重合体 (Α)は、通 常のランダム性良好な共重合体に比較して、不均一性が高ぐ同一不飽和エステル 単位含有量のもので比較して融点が高い。このような共重合体は、例えば高圧ラジカ ル重合法において、オートクレープ法で多段重合するかあるいはチューブラー法に よって製造することができる。これら製法の一例として、特開昭 62— 273214号ゃ特 許第 3423308号の各公報に紹介された方法を挙げることができる。  A copolymer satisfying the above is preferably used. In the present invention, X is preferably in the range of 0.5 to 12.2. The ethylene 'unsaturated ester copolymer (Α) that satisfies this formula is compared with a copolymer with the same unsaturated ester unit content that has higher heterogeneity compared to a copolymer with good randomness. And the melting point is high. Such a copolymer can be produced, for example, by a multistage polymerization by an autoclave method or a tubular method in a high pressure radical polymerization method. As an example of these production methods, the methods introduced in JP-A-62-273214 and Japanese Patent No. 3423308 can be mentioned.
[0026] 本発明のエラストマ一（Β)としてはまた、スチレン系熱可塑性エラストマ一を使用す ることができる。スチレン系熱可塑性エラストマ一としては、スチレン系モノマーを主体 とする重合体ブロック (X)と共役ジェンィ匕合物を主体とするブロック (Υ)のブロック共 重合体及び該ブロック共重合体の共役ジェン重合単位を水素添加したものを例示 することができる。ここにスチレン系モノマーとしては、スチレン、 a—メチノレスチレン、 ビュルトルエン、 tーブチルスチレンなどを例示することができる力 とくにスチレンが 好ましい。また共役ジェン化合物としては、ブタジエン、イソプレン、クロ口プレン、 2, 3—ジメチルブタジエンなどを例示することができる力 とくにブタジエン又はイソプレ ンが好ましい。 [0026] As the elastomer (Β) of the present invention, a styrenic thermoplastic elastomer can also be used. As the styrene-based thermoplastic elastomer, a block copolymer of a polymer block (X) mainly composed of a styrene-based monomer and a block (共 役) mainly composed of a conjugated-gene compound and a conjugated gene of the block copolymer are used. Examples include those obtained by hydrogenating polymerized units. Here, as the styrenic monomer, styrene, a-methylol styrene, butyl toluene, t-butyl styrene and the like can be exemplified, and styrene is particularly preferable. Further, as the conjugated-gen compound, butadiene, isoprene, butadiene, isoprene, and the like are particularly preferable, since they are exemplified by butadiene, isoprene, black-opened plane, 2,3-dimethylbutadiene and the like.
[0027] スチレン系モノマーを主体とする重合体ブロック (X)と共役ジェン化合物を主体と する重合体ブロック (Y)のブロック共重合体としては、例えば、（X—Y) 又は (X—Y) X (式中、 nは 1以上の整数)で表される直鎖状、分岐状、放射状のブロック共重合 体を挙げることができる。スチレン系モノマー重合体ブロックが 10〜60重量％、共役 ジェン重合体ブロックが 90〜40重量％程度のブロック共重合体又はその水素添カロ 物がその代表的なものである。 [0028] スチレン系熱可塑性エラストマ一としては、ォレフィン性二重結合ができるだけ少な いものが望ましぐ上記スチレン系モノマーを主体とする重合体ブロックと共役ジェン 化合物を主体とする重合体ブロック力 なるブロック共重合体の共役ジェン重合単位 の 70%以上、好ましくは 90%以上が水素添加されたものが好ましい。より具体的に は、共役ジェンィ匕合物を主体とする重合体ブロックにおける 1, 2 又は 3, 4 など のビュル結合が 10%以上、好ましくは 20〜80%、一層好ましくは 30〜60%のブロ ック共重合体が水素添加されたスチレン系化合物含量が 8〜50重量％、好ましくは 1 0〜40重量％の水素添カ卩ブロック共重合体であって、例えば X— Y'— X型ブロック 共重合体が最適である。ここに Xはスチレン系重合体ブロックを、また Y'は水素添カロ 共役ジェン重合体ブロック、すなわちアルキレン共重合体ブロック、具体的にはェチ レン ·ブテン共重合体ブロックあるいはエチレン 'プロピレン共重合体ブロックなどであ る。このようなブロック共重合体は、一般に SBSと称されているスチレン一ブタジエン 一スチレンブロック共重合体ある 、は SISと称されて!/、るスチレン一イソプレンースチ レンブロック共重合体のブタジエン重合体ブロックあるいはイソプレン重合体ブロック を水素添カ卩して得られるものであって、一般に SEBSある!/、は SEPSと称せられて!/ヽ るものである。熱可塑性スチレン系エラストマ一としては、 200°C、 5kg荷重におけるメ ノレ卜フローレ一卜（ASTM D1238)力 0. l〜500g/10分、とくに 0. 5〜150g/10 分程度のものを使用するのが好ましい。これらは例えば、クレイトン 1101 (SBS)、ク レイ卜ン 1102 (SBS)、クレイ卜ン 1107 (313)、クレィ卜ン4122 (3 3)、クレィ卜ン016 51 (SEBS)、クレイトン G1652 (SEBS)、クレイトン G1657 (SEBS)などの商品名の ものを使用することができる。 [0027] Examples of the block copolymer of the polymer block (X) mainly composed of a styrene monomer and the polymer block (Y) mainly composed of a conjugated diene compound include (X—Y) or (X—Y). And a linear, branched, and radial block copolymer represented by X (wherein n is an integer of 1 or more). A typical example is a block copolymer of about 10 to 60% by weight of a styrene monomer polymer block and about 90 to 40% by weight of a conjugated polymer block or a hydrogenated carbohydrate thereof. [0028] As the styrenic thermoplastic elastomer, those having as few olefinic double bonds as possible are desirable. The polymer block mainly composed of the styrene monomer and the polymer block mainly composed of a conjugated diene compound are used. It is preferred that 70% or more, preferably 90% or more, of the conjugation polymer units of the block copolymer are hydrogenated. More specifically, in the polymer block mainly composed of conjugated diene compounds, the bull bonds such as 1, 2 or 3, 4 are 10% or more, preferably 20 to 80%, more preferably 30 to 60%. A hydrogenated block copolymer having a styrene compound content of hydrogenated block copolymer of 8 to 50% by weight, preferably 10 to 40% by weight, for example, X—Y′—X A mold block copolymer is optimal. Where X is a styrenic polymer block, and Y 'is a hydrogenated caroconjugated polymer block, that is, an alkylene copolymer block, specifically an ethylene / butene copolymer block or an ethylene' propylene copolymer block. For example, a merged block. Such a block copolymer is a styrene-butadiene-styrene block copolymer, commonly referred to as SBS, or SIS! /, A butadiene polymer block of a styrene-isoprenestyrene block copolymer. Alternatively, it is obtained by hydrogenating an isoprene polymer block, and generally SEBS! / Is called SEPS! /. As thermoplastic styrene elastomers, use one that has a male flow (ASTM D1238) force of 0.1 to 500 g / 10 min at 200 ° C and 5 kg load, especially about 0.5 to 150 g / 10 min. It is preferable to do this. These include, for example, Clayton 1101 (SBS), Crane 1102 (SBS), Crane 1107 (313), Crane 4122 (3 3), Crane 016 51 (SEBS), Clayton G1652 (SEBS) A product with a trade name such as Clayton G1657 (SEBS) can be used.
[0029] 本発明のエチレン共重合体組成物に使用することができる結晶性ポリオレフイン (C )は、 X線における結晶化度が 40%を超えるォレフィンの単独重合体又はォレフィン 同士の共重合体であって、具体的には各種密度のポリエチレン、ポリプロピレン、ポリ — 1—ブテン、ポリ一 4—メチル 1—ペンテンなどを挙げることができる。これらの中 ではポリエチレン、中でも直鎖低密度ポリエチレンを用いる力 あるいはポリプロピレ ンを使用することが好ましい。  [0029] The crystalline polyolefin (C) that can be used in the ethylene copolymer composition of the present invention is an olefin homopolymer or a copolymer of olefins having a crystallinity of 40% or more in X-rays. Specific examples include polyethylene, polypropylene, poly-1-butene, poly-4-methyl 1-pentene, and the like having various densities. Among these, it is preferable to use the force using polyethylene, especially linear low density polyethylene, or polypropylene.
[0030] 上記直鎖低密度ポリエチレンは、エチレンと炭素数 3以上、好ましくは 3〜 12の α —ォレフインの共重合体であって、密度力 90〜940kgZm3、好ましくは 900〜93 OkgZm3のものである。これらはシクロペンタジェニル骨格を有する配位子を有する ジルコニウムの化合物からなるメタ口セン触媒成分と有機アルミニウムォキシィ匕合物 触媒成分の組み合わせ触媒のようなシングルサイト触媒、ある ヽは高活性チタン触 媒成分と有機アルミニウム化合物触媒成分の組み合わせ触媒のようなマルチサイト 触媒の存在下に、エチレンと炭素数 3以上の α—ォレフィン、例えばプロピレン、 1 ブテン、 1—ペンテン、 1—へキセン、 1—オタテン、 1—デセン、 1—ドデセン、 4—メ チルー 1 ペンテンなどを共重合することによって製造することができる。とくにシング ルサイト触媒を用いて得られる直鎖低密度ポリエチレンが好適である。直鎖低密度ポ リエチレンとしてはまた、他成分との混和性や加工性を考慮すると、 190°C、 2160g 荷重におけるメノレ卜フローレ一卜（ASTM D1238)力^). l〜500g/10分、とくに 0. 5〜150gZlO分のものを使用することが好ましい。 [0030] The linear low density polyethylene is ethylene and α having 3 or more carbon atoms, preferably 3 to 12 carbon atoms. —A copolymer of olefin, having a density force of 90 to 940 kgZm 3 , preferably 900 to 93 OkgZm 3 . These are single-site catalysts such as a combination catalyst of a meta-octane catalyst component composed of a compound of zirconium having a ligand having a cyclopentadenyl skeleton and an organoaluminum oxide catalyst component. In the presence of a multisite catalyst such as a combination catalyst of a titanium catalyst component and an organoaluminum compound catalyst component, ethylene and an α-olefin having 3 or more carbon atoms such as propylene, 1 butene, 1-pentene, 1-hexene, It can be produced by copolymerizing 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and the like. In particular, linear low density polyethylene obtained using a single site catalyst is preferred. As for linear low density polyethylene, considering the miscibility with other components and processability, it is 190 ° C, 2160g load Menore-Floret (ASTM D1238) force ^). L ~ 500g / 10min, In particular, it is preferable to use one having a content of 0.5 to 150 gZlO.
[0031] ポリオレフイン（C)として好適なポリプロピレンは、プロピレン単独重合体又はプロピ レンを主体とするプロピレンとその他の a—ォレフインとの共重合体であって、密度は 870〜930kg/m3、とくに 880〜920kg/m3のもの力好まし!/、。また 230°C、 2160 g荷重におけるメルトフローレート（ASTM D1238)カ^). l〜500gZlO分、とくに 0 . 5〜150gZlO分のもの力 S好ましい。上記プロピレンの共重合体においてプロピレ ンと共重合される α—ォレフインとしては、炭素数 2〜12、とくに炭素数 2〜： LOのもの が好ましぐ具体的には、エチレン、 1—ブテン、 1—へキセン、 1—オタテン、 1—デセ ン、 1ードデセン、 4ーメチルー 1 ペンテンなどの 1種又は 2種以上を例示することが できる。このようなプロピレン' a—ォレフイン共重合体中の a—ォレフイン単位の含 有量は、 20モル0 /0以下、とくに 0. 1〜15モル0 /0であることが好ましい。該プロピレン 共重合体は、ランダム共重合体でもブロック共重合体であってもよい。これらポリプロ ピレンは、立体規則性ォレフイン重合触媒の存在下にプロピレンを重合又は共重合 すること〖こよって得ることができる。 [0031] Polypropylene suitable as polyolefin (C) is a propylene homopolymer or a copolymer of propylene mainly composed of propylene and other a-olefin, and has a density of 870 to 930 kg / m 3 , in particular. 880-920kg / m 3 is preferred! Also, a melt flow rate at 230 ° C and a load of 2160 g (ASTM D1238) ^). 1 to 500 gZlO, particularly 0.5 to 150 gZlO. The α-olefins copolymerized with propylene in the propylene copolymer are those having 2 to 12 carbon atoms, particularly those having 2 to carbon atoms: LO, specifically, ethylene, 1-butene, Examples thereof include one or more of 1-hexene, 1-octene, 1-decene, 1-decene, 4-methyl-1-pentene, and the like. Such propylene 'containing Yuryou of a- Orefuin copolymer of a- Orefuin units, 20 mole 0/0 or less, particularly preferably 0.1 to 15 mole 0/0. The propylene copolymer may be a random copolymer or a block copolymer. These polypropylenes can be obtained by polymerizing or copolymerizing propylene in the presence of a stereoregular polyolefin polymerization catalyst.
[0032] 本発明のエチレン共重合体組成物に使用することができる粘着付与榭脂 (D)は、 脂肪族系炭化水素榭脂、脂環族系炭化水素榭脂、芳香族系炭化水素榭脂、ポリテ ルペン系榭脂、ロジン類、スチレン系榭脂、クマロン'インデン榭脂などを挙げること ができる。脂肪族系炭化水素榭脂の例としては、 1—ブテン、イソブテン、ブタジエン 、 1, 3 ペンタジェン、イソプレンなど炭素数 4〜5のモノ又はジォレフインの少なくと も 1種以上を含む留分を重合して得られる榭脂を挙げることができる。脂環族系炭化 水素樹脂の例として、スベント C〜C留分中のジェン成分を環化二量ィ匕後重合させ [0032] The tackifier resin (D) that can be used in the ethylene copolymer composition of the present invention includes an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, and an aromatic hydrocarbon resin. Examples include fats, polyethylene pens, rosins, styrenes, coumarone and indene Can do. Examples of aliphatic hydrocarbon resins include 1-butene, isobutene, butadiene, 1,3 pentagen, isoprene and other fractions containing at least one kind of mono- or diolefins having 4 to 5 carbon atoms. Can be mentioned. As an example of an alicyclic hydrocarbon resin, the gen component in the subent C to C fraction is polymerized after cyclization dimerization.
4 5  4 5
て得られる榭脂、シクロペンタジェンなどの環状モノマーを重合させた榭脂、芳香族 系炭化水素榭脂を核内水添した榭脂などを挙げることができる。  Examples thereof include a resin obtained by polymerizing cyclic monomers such as cyclopentagen, and a resin obtained by hydrogenating an aromatic hydrocarbon resin.
[0033] 芳香族系炭化水素榭脂の例として、ビュルトルエン、インデン、 α—メチルスチレン などの C〜C のビニル芳香族炭化水素を少なくとも一種以上含有する留分を重合[0033] As an example of an aromatic hydrocarbon resin, a fraction containing at least one C to C vinyl aromatic hydrocarbon such as butyltoluene, indene, and α-methylstyrene is polymerized.
8 10 8 10
して得られる榭脂、ある 、はこれら留分と上記脂肪族炭化水素留分を共重合して得 られる榭脂などを挙げることができる。ポリテルペン系榭脂の例としては、 a ピネン 重合体、 j8—ピネン重合体、ジペンテン重合体、テルペン'フヱノール共重合体、 α —ビネン 'フ ノール共重合体、これらの水素添加物などを挙げることができる。  Examples of the resin can be obtained by copolymerizing these fractions and the above aliphatic hydrocarbon fractions. Examples of polyterpene-based resin include a pinene polymer, j8-pinene polymer, dipentene polymer, terpene'phenol copolymer, α-vinene'phenol copolymer, and hydrogenated products thereof. Can do.
[0034] ロジン類としては、ガムロジン、ウッドロジン、トール油などのロジン及びその変性物 などであり、変性物としては水素添加、不均化、二量化、エステル化などの変性を施 したものを例示することができる。スチレン系炭化水素榭脂としては、純度の高いスチ レン、ビュルトルエン、 α—メチルスチレン、イソプロピルトルエンなどのスチレン系単 量体の 1種又は 2種以上を重合して得られる分子量の低 、榭脂状重合体を挙げるこ とがでさる。 [0034] Examples of rosins include gum rosin, wood rosin, tall oil and other modified rosins, and modified products thereof. Examples of modified products include those that have undergone modification such as hydrogenation, disproportionation, dimerization, and esterification. can do. Styrenic hydrocarbon resin has a low molecular weight and is obtained by polymerizing one or more styrene monomers such as high-purity styrene, butyltoluene, α -methylstyrene, and isopropyltoluene. Mention may be made of oily polymers.
[0035] 本発明のエチレン共重合体組成物を飲食品包装用の易開封性シール材料として 使用する場合には、無臭性、食品衛生性、他成分との混和性などを考慮すると、芳 香族系炭化水素榭脂ゃテルペン榭脂などの炭化水素榭脂を水素添加した榭脂を使 用することが好ましい。  [0035] When the ethylene copolymer composition of the present invention is used as an easily-openable sealing material for packaging foods and drinks, considering the odorlessness, food hygiene, miscibility with other components, etc. It is preferable to use a resin obtained by hydrogenating a hydrocarbon resin such as a terpene resin.
[0036] 本発明のエチレン共重合体組成物におけるエチレン ·不飽和エステル共重合体 (A )の配合割合は、 40〜98重量部、好ましくは 40〜95重量部、さらに好ましくは 50〜 90重量部、エラストマ一（B)の配合割合は、 60〜0重量部、好ましくは 60〜2重量部 、さらに好ましくは 50〜 10重量部、結晶性ポリオレフイン (C)の配合割合は、 30〜0 重量部、好ましくは 30〜2重量部、さらに好ましくは 20〜5重量部、および粘着付与 剤（D)の配合割合は 0〜30重量部の範囲であることが好ま 、が、 (B)と (C)の合計 量は 2〜60重量部であることが必要である [ただし (A)、（B)、（C)、（D)の合計量は 100重量部である]。 The blending ratio of the ethylene / unsaturated ester copolymer (A) in the ethylene copolymer composition of the present invention is 40 to 98 parts by weight, preferably 40 to 95 parts by weight, more preferably 50 to 90 parts by weight. Part, the blending ratio of the elastomer (B) is 60 to 0 parts by weight, preferably 60 to 2 parts by weight, more preferably 50 to 10 parts by weight, and the blending ratio of the crystalline polyolefin (C) is 30 to 0 parts by weight. Parts, preferably 30 to 2 parts by weight, more preferably 20 to 5 parts by weight, and the proportion of the tackifier (D) is preferably in the range of 0 to 30 parts by weight, but (B) and ( C) total The amount should be 2-60 parts by weight [however, the total amount of (A), (B), (C), (D) is 100 parts by weight].
[0037] 本発明のエチレン共重合体組成物には、さらにエチレン共重合体組成物中の重合 体成分 (A)、（B)及び (C)の合計量 100重量部に対し 10重量部まで、好ましくは 0. 01〜10重量部の防曇剤 (E)を配合することができる。防曇剤を配合することによつ て、防曇性に優れ、ポリプロピレンやポリスチレンなどの炭化水素系重合体に対して、 適度なヒートシール強度を有し、ヒートシール強度の温度依存性も少なぐ低温でヒ ートシールすることが可能な易開封性シール材料の提供を可能とするエチレン共重 合体組成物を得ることができる。  [0037] The ethylene copolymer composition of the present invention further includes up to 10 parts by weight with respect to 100 parts by weight of the total amount of the polymer components (A), (B) and (C) in the ethylene copolymer composition. Preferably, 0.01 to 10 parts by weight of the antifogging agent (E) can be blended. By adding an antifogging agent, it has excellent antifogging properties, has moderate heat seal strength against hydrocarbon polymers such as polypropylene and polystyrene, and has little temperature dependence of heat seal strength. It is possible to obtain an ethylene copolymer composition that makes it possible to provide an easy-open sealing material that can be heat-sealed at a low temperature.
[0038] 防曇剤 (E)としては、非イオン系、ァ-オン系及びカチオン系の界面活性剤を使用 することができる。例えば、ポリオキシアルキレンエーテル、多価アルコールの部分ェ ステル、多価アルコールのアルキレンオキサイド付カ卩物の部分エステル、ポリ（ォキシ エチレン）アルキルァミン、ポリ（ォキシエチレン）アルキルアミド、高級アルコール硫 酸エステルアルカリ金属塩、アルキルァリールスルホネート、四級アンモ-ゥム塩など を挙げることができる。より具体的には、ポリオキシエチレンラウリルエーテル、ポリオ キシエチレンステアリルエーテル、ポリオキシエチレンノニルフエニルエーテル、ポリ エチレングリコールモノパルミテート、ポリエチレングリコールモノステアレート、ポリオ キシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート 、グリセリンモノラウレート、グリセリンモノパルミテート、グリセリンモノステアレート、グリ セリンモノォレート、ペンタエリスリトーノレモノラウレート、ソルビタンモノパルミテート、ソ ルビタンモノべへネート、ソルビタンモノステアレート、ソルビタンジステアレート、ジグ リセリンモノォレート、トリグリセリンジォレート、ナトリウムラウリルサルフェート、ドデシ ルベンゼンスルホン酸ナトリウム、ブチルナフタレンスルホン酸ナトリウム、セチルトリメ チルアンモ -ゥムクロライド、トリメチルベンジルアンモ -ゥムクロライド、トリェチルセチ ルアンモ-ゥムィオダイド、ドデシルァミン塩酸塩、ラウリン酸ラウリルアミドエチルリン 酸塩、ォレイルアミノジェチルァミン塩酸塩、ドデシルピリジ -ゥム硫酸塩などを挙げ ることができる。これらの中では非イオン系界面活性剤を使用するのが好ましぐとく に多価アルコールのエステル、とりわけ、ポリエチレングリコール、グリセリン、ジグリセ リン及びソルビタンから選ばれる多価アルコールの脂肪酸エステルを使用するのが 好ましい。これらは 2種以上併用することができる。 [0038] As the antifogging agent (E), nonionic, ionic and cationic surfactants can be used. For example, polyoxyalkylene ether, partial ester of polyhydric alcohol, partial ester of polyhydric alcohol with alkylene oxide, poly (oxyethylene) alkylamine, poly (oxyethylene) alkylamide, higher alcohol sulfate alkali metal Salt, alkylaryl sulfonate, quaternary ammonium salt and the like. More specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan monopalmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, pentaerythritolol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monostearate, Sorbitan distearate, diglyceryl monooleate, triglyceryl dioleate, sodium lauryl sulfate, dodecylbenzenesulfo Sodium acetate, sodium butylnaphthalenesulfonate, cetyltrimethylammo-muchloride, trimethylbenzylammo-chloride, triethylcetylammooxide, dodecylamine hydrochloride, lauryl lauramidoethyl phosphate, oleylaminojetylamine hydrochloride, dodecylpyridi- Examples thereof include um sulfate. Of these, it is preferable to use nonionic surfactants, particularly esters of polyhydric alcohols, especially polyethylene glycol, glycerin, diglyceride. It is preferable to use a fatty acid ester of a polyhydric alcohol selected from phosphorus and sorbitan. Two or more of these can be used in combination.
[0039] 本発明のエチレン共重合体組成物においては、任意に各種添加剤を配合すること ができる。力かる添加剤の代表例としては、押出加工性、離ロール性、フィルムの滑り 性などを改善する目的で使用される滑剤及び Z又は離ロール剤を挙げることができ る。より具体的には、パルミチン酸アミド、ステアリン酸アミド、ベへニン酸アミド、ォレイ ン酸アミド、エル力酸アミド、ォレイルパルミドアミド、ステアリルパルミドアミド、メチレン ビスステアリルアミド、メチレンビスォレイルアミド、エチレンビスォレイルアミド、ェチレ ンビスエル力酸アミドなどの各種アミド類、ポリエチレングリコール、ポリプロピレンダリ コールなどのポリアルキレングリコール、水添ひまし油、シリカ、タルクなどの無機質添 加剤などである。これらの組成物中の配合量は、無機質添加剤の場合は 0〜3重量 %、好ましくは 0. 1〜3重量％程度、それ以外のものは 0〜1重量％、好ましくは 0. 0 1〜 1重量％程度の範囲が適当である。  [0039] In the ethylene copolymer composition of the present invention, various additives can be optionally blended. Representative examples of such additives include lubricants used for the purpose of improving extrudability, roll release properties, film slip properties and the like, and Z or roll release agents. More specifically, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, L force acid amide, oleyl palmidamide, stearyl palmamide, methylene bisstearylamide, methylenebisoleylamide, These include various amides such as ethylenebisoleamide and ethylene bisphenol amide, polyalkylene glycols such as polyethylene glycol and polypropylene darcol, hydrogenated castor oil, silica, talc and other inorganic additives. The blending amount in these compositions is 0 to 3% by weight, preferably about 0.1 to 3% by weight in the case of inorganic additives, and 0 to 1% by weight, preferably 0.01% in other cases. A range of about 1% by weight is appropriate.
[0040] 任意に配合し得る他の添加剤の例としては、粘着付与榭脂、酸化防止剤、熱安定 剤、光安定剤、顔料、染料などを例示することができる。粘着付与榭脂は、シール強 度の微調整を行うのに有用である。粘着付与榭脂としては例えば、脂肪族系炭化水 素榭脂、脂環族系炭化水素榭脂、芳香族系炭化水素榭脂、ポリテルペン系榭脂、口 ジン類、スチレン系榭脂、クマロン'インデン榭脂などを挙げることができる。脂肪族系 炭化水素榭脂の例としては、 1ーブテン、イソブテン、ブタジエン、 1, 3—ペンタジェ ン、イソプレンなど炭素数 4〜5のモノ又はジォレフインの少なくとも 1種以上を含む留 分を重合して得られる榭脂を挙げることができる。脂環族系炭化水素榭脂の例として 、スベント C〜C留分中のジェン成分を環化二量ィ匕後重合させて得られる榭脂、シ  [0040] Examples of other additives that can be optionally blended include tackifier resins, antioxidants, heat stabilizers, light stabilizers, pigments, and dyes. Tackifying resin is useful for fine adjustment of seal strength. Examples of tackifier resins include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, oral resins, styrene resins, and coumarones. Inden rosin can be used. Examples of aliphatic hydrocarbon resin include polymerizing a fraction containing at least one kind of mono- or olefins having 4 to 5 carbon atoms such as 1-butene, isobutene, butadiene, 1,3-pentagen, and isoprene. Mention may be made of the resulting rosin. As an example of alicyclic hydrocarbon resin, a resin obtained by polymerizing a gen component in a subent C to C fraction after cyclization dimerization and polymerization is used.
4 5  4 5
クロペンタジェンなどの環状モノマーを重合させた榭脂、芳香族系炭化水素榭脂を 核内水添した榭脂などを挙げることができる。  Examples thereof include a resin obtained by polymerizing a cyclic monomer such as clopentagen, and a resin obtained by hydrogenating an aromatic hydrocarbon resin.
[0041] 本発明のエチレン共重合体組成物は、本発明にしたがって上記 (A)〜(E)から選 ばれる成分及び必要に応じて配合されるその他添加剤を、同時に又は逐次的に混 合することによって調製することができる。エチレン共重合体組成物を調製するに当 たっては、単軸押出機、二軸押出機、バンバリ一ミキサー、各種-一ダーなどを用い て、例えば 130〜230°Cで溶融混合するのが好ましぐその混合順序にはとくに制限 はない。 [0041] In the ethylene copolymer composition of the present invention, components selected from the above (A) to (E) according to the present invention and other additives blended as necessary are mixed simultaneously or sequentially. Can be prepared. In preparing the ethylene copolymer composition, a single screw extruder, a twin screw extruder, a Banbury mixer, various types, etc. are used. For example, it is preferable to melt and mix at 130 to 230 ° C., and the mixing order is not particularly limited.
[0042] 力べして得られる本発明のエチレン共重合体組成物は、押出加工性、シール強度 等を考慮すると、 190°C、 2160g荷重におけるメルトフローレート (JIS K7210- 19 99)が l〜400gZl〇分、とくに l〜150gZl〇分程度となるように調製されていること が望ましい。  [0042] The ethylene copolymer composition of the present invention obtained by force has a melt flow rate (JIS K7210-19999) at 190 ° C and a load of 2160 g, considering extrusion processability, seal strength, and the like. It is desirable that it be prepared to be 400 gZlOmin, especially about 1 to 150gZlOmin.
[0043] 本発明のエチレン共重合体組成物は、易開封性シール材料、とくに包装材料の易 開封性シール材料、とりわけポリプロピレンやポリスチレンなどの炭化水素系重合体 に対する易開封性シール材料として好適である。易開封性シール材料に使用される 場合、通常は各種基材に積層した形で使用される。カゝかる目的に使用される基材と しては、紙、アルミニウム、ポリエステル、ポリエチレン、ポリプロピレン、（高衝撃）ポリ スチレン、アルミ蒸着ポリエステル、アルミ蒸着ポリプロピレン、シリカ蒸着ポリエステ ルなどを挙げることができる。このような基材は単層である必要はなぐ 2層以上の積 層体であってもよい。  [0043] The ethylene copolymer composition of the present invention is suitable as an easily openable seal material, particularly as an easily openable seal material for packaging materials, especially as an easily openable seal material for hydrocarbon polymers such as polypropylene and polystyrene. is there. When used as an easy-open seal material, it is usually used in a form laminated to various substrates. Examples of the base material used for the purpose of making a cover include paper, aluminum, polyester, polyethylene, polypropylene, (high impact) polystyrene, aluminum-deposited polyester, aluminum-deposited polypropylene, and silica-deposited polyester. . Such a substrate need not be a single layer, and may be a laminate of two or more layers.
[0044] 本発明のエチレン共重合体組成物を基材に積層させるには、該組成物を予めキヤ スト法やインフレーション法によりフィルム化し、ドライラミネーシヨン法により基材と貼り 合わせる方法、該組成物を直接基材上に押出コーティングする方法、ポリエチレン等 を接着層として用い、基材上にサンドイツチラミネーシヨンにより接着層を介して積層 する方法、基材と該組成物を共押出する方法などを採用することができる。  [0044] In order to laminate the ethylene copolymer composition of the present invention on a substrate, the composition is previously formed into a film by a casting method or an inflation method, and bonded to the substrate by a dry lamination method, the composition A method of extrusion-coating a product directly onto a substrate, a method of using polyethylene or the like as an adhesive layer, a method of laminating on a substrate with an adhesive layer through a sand layer, a method of co-extrusion of a substrate and the composition Etc. can be adopted.
[0045] 力べして得られる積層体は、各種包装材料として使用することができる。とくに各種 容器、とりわけポリプロピレン製容器やポリスチレン製容器の蓋材として使用するとき に、防曇性、密封性、易開封性等に優れた蓋材となる。またこれら炭化水素系重合 体の容器のみならず、他の材料の容器、例えば、ポリエステル、ポリカーボネート、ポ リ塩ィ匕ビュル等の容器の蓋材としても利用できる。このような蓋付容器は、例えば、ゼ リー、プリン、ヨーグルト、みつ豆、サワー、豆腐、乳酸飲料、和菓子、加工肉などの飲 食物、薬品、医療容器、トナーなどの各種包装に使用することができる。  [0045] The laminate obtained by force can be used as various packaging materials. In particular, when used as a cover material for various containers, especially polypropylene containers and polystyrene containers, it is a cover material having excellent antifogging properties, sealing properties, and easy-opening properties. Further, it can be used not only as a container for these hydrocarbon polymers, but also as a cover material for containers made of other materials, for example, containers of polyester, polycarbonate, polysalt gel, etc. Such a container with a lid can be used, for example, for various packaging of foods such as jelly, pudding, yogurt, honey bean, sour, tofu, lactic acid beverage, Japanese confectionery, processed meat, medicines, medical containers, and toner it can.
実施例  Example
[0046] 以下、実施例により本発明をさらに詳細に説明する。尚、実施例及び比較例にお いて用いた原料は、以下の通りである。 [0046] Hereinafter, the present invention will be described in more detail by way of examples. In the examples and comparative examples, The raw materials used were as follows.
1 原料  1 Raw material
(1)エチレン ·不飽和エステル共重合体 (A)  (1) Ethylene / unsaturated ester copolymer (A)
EMA：エチレン'アクリル酸メチル共重合体（アクリル酸メチル単位含有量 20重量0 /0 、メルトフローレート（190。C、 2160g荷重、 JIS K7210— 1999) 8gZlO分、融点 9 2°C) EMA: ethylene 'methyl acrylate copolymer (methyl acrylate unit content 20 wt 0/0, melt flow rate (190.C, 2160 g load, JIS K7210- 1999) 8gZlO fraction, mp 9 2 ° C)
(2)エラストマ一 (B)  (2) Elastomer (B)
SEBS：スチレン'エチレン/ブテン ·スチレンブロック共重合体（商品名：クレイトン G 1657、スチレン重合体ブロック 13重量0 /0、エチレン Zブテン重合体ブロック 87重量 %、メルトフローレート（200。C、 5kg、 ASTM D1938) 8g/10分） SEBS: Styrene 'ethylene / butene-styrene block copolymer (trade name: Kraton G 1657, styrene polymer block 13 weight 0/0, ethylene Z butene polymer block 87 wt%, melt flow rate (200.C, 5 kg , ASTM D1938) 8g / 10min)
(3)結晶性ポリオレレン (C)  (3) Crystalline polyolefin (C)
(a) mPE 1：シングルサイト触媒で製造した直鎖低密度ポリエチレン (商品名：ェボ リュー SC00100、三井ィ匕学 (株）製、密度 902kgZm3、メル卜フローレ一卜（190。C、 2160g荷重、 ASTM D1238) 8gZlO分） (a) mPE 1: Linear low-density polyethylene manufactured with a single-site catalyst (trade name: Evolue SC00100, manufactured by Mitsui Engineering Co., Ltd., density 902kgZm 3 , Mel-Floret (190.C, 2160g Load, ASTM D1238) 8gZlO min)
(b) mPE 2：シングルサイト触媒で製造した直鎖低密度ポリエチレン (商品名：ェボ リュー SP0540、三井ィ匕学 (株）製、密度 903kgZm3、メルトフローレート（190。C、 2 160g荷重、 ASTM D1238) 3. 8gZlO分） (b) mPE 2: Linear low-density polyethylene produced with a single site catalyst (trade name: Evolue SP0540, manufactured by Mitsui Chemicals, Ltd., density 903kgZm 3 , melt flow rate (190.C, 2 160g load) , ASTM D1238) 3. 8gZlO min)
(c) PP：プロピレン ·エチレン · 1 ブテンランダム共重合体（エチレン単位含有量 3. 6モル％(2. 4重量％)、 1ーブテン単位含有量 1. 9モル％(2. 5重量％)、密度 910
Figure imgf000014_0001
メル卜フローレ一卜（230。C、 2160g荷重、 ASTM D1238) 6gZlO分）(c) PP: propylene / ethylene / 1 butene random copolymer (ethylene unit content 3.6 mol% (2.4 wt%), 1-butene unit content 1.9 mol% (2.5 wt%) , Density 910
Figure imgf000014_0001
Mel floret (230C, 2160g load, ASTM D1238) 6gZlO min)
(4)粘着付与樹脂 (D) (4) Tackifying resin (D)
P115 :水素添加芳香族炭化水素榭脂 (商品名：アルコン AMI (荒川化学 (株)製、 環球法軟化点 115°C)  P115: Hydrogenated aromatic hydrocarbon resin (trade name: Archon AMI (Arakawa Chemical Co., Ltd., ring and ball softening point 115 ° C)
(5)防曇剤 (E)  (5) Antifogging agent (E)
ジグリセリン脂肪酸エステル (商品名：リケマール 0— 71— DE、理研ビタミン (株） 製）  Diglycerin fatty acid ester (trade name: Riquemar 0— 71— DE, manufactured by Riken Vitamin Co., Ltd.)
[実施例 1〜10、参考例]  [Examples 1 to 10, reference examples]
ヱチレン共重合体組成物の製诰 表 1に示す配合組成比で各成分を、単軸押出機を用いて 150°Cで溶融混練して組 成物を製造した。 诰 Making styrene copolymer composition Each component was melt-kneaded at 150 ° C. using a single screw extruder at the composition ratio shown in Table 1 to produce a composition.
次に予め作成した延伸 PET (厚さ 12 μ m) Z低密度ポリエチレン (厚さ 20 μ m)から なる 2層構成の積層フィルムのポリエチレンフィルム面側に、表 1に示す配合組成の エチレン共重合体組成物を押出ラミネーシヨンにより 30 m厚みで積層し、試験基 材を得た。  Next, on the polyethylene film surface side of a two-layer laminated film made of stretched PET (thickness 12 μm) Z low-density polyethylene (thickness 20 μm), the ethylene copolymer of the composition shown in Table 1 The coalesced composition was laminated by extrusion lamination to a thickness of 30 m to obtain a test substrate.
[0048] 厚さ 300 μ mのポリプロピレンシート又はポリスチレンシートにこの試験基材をその エチレン共重合体組成物面が当接するように重ね合わせ、 120°C、 140°C及び 160 °Cの温度、圧力 0. 2MPa、シール時間 1. 0秒の条件でヒートシールして積層体を得 た。この積層体力も試験基材部を剥離したときの剥離強度を測定した。これらの結果 を表 1に併記する。  [0048] The test substrate was superposed on a 300 μm-thick polypropylene sheet or polystyrene sheet so that the ethylene copolymer composition surface abuts it, and temperatures of 120 ° C., 140 ° C. and 160 ° C., The laminate was obtained by heat sealing under the conditions of pressure 0.2 MPa and sealing time 1.0 seconds. The laminate strength was also measured for peel strength when the test substrate was peeled off. These results are also shown in Table 1.
[0049] [表 1] [0049] [Table 1]
Figure imgf000016_0001
Figure imgf000016_0001
[0050] [実施例 11〜12、比較例 1] [0050] [Examples 11 to 12, Comparative Example 1]
ヱチレン共重合体組成物の製诰  诰 Making styrene copolymer composition
表 2に示す配合組成比で各成分を、単軸押出機を用いて、 150°Cで溶融混練して 組成物を製造した。  Each component was melt kneaded at 150 ° C. using a single-screw extruder at the composition ratio shown in Table 2 to produce a composition.
次に予め作成した延伸 PET (厚さ 12 μ m) Z低密度ポリエチレン (厚さ 20 μ m)から なる 2層構成の積層フィルムのポリエチレンフィルム面側に、表 2に示す配合組成の エチレン共重合体組成物を押出ラミネーシヨンにより 30 m厚みで積層し、試験基 材を得た。この試験基材を、冷蔵庫において 5°Cで 1週間保管したときの防曇性を目 視により評価した。  Next, on the polyethylene film surface side of a two-layer laminated film made of stretched PET (thickness 12 μm) Z low-density polyethylene (thickness 20 μm), ethylene copolymer having the composition shown in Table 2 The coalesced composition was laminated by extrusion lamination to a thickness of 30 m to obtain a test substrate. This test substrate was visually evaluated for antifogging properties when stored in a refrigerator at 5 ° C for 1 week.
〇：曇りなし  ○: No cloudiness
X：曇りあり  X: Cloudy
[0051] また厚さ 300 μ mのポリスチレンシートにこの試験基材をそのエチレン共重合体組 成物面が当接するように重ね合わせ、 120°C、 140°C及び 160°Cの温度、圧力 0.2 MPa、シール時間 1.0秒の条件でヒートシールして積層体を得た。この積層体から 試験基材部を剥離したときの剥離強度を測定した。これらの結果を表 2に併記する。  [0051] The test substrate was placed on a 300 μm thick polystyrene sheet so that the ethylene copolymer composition surface was in contact with it, and the temperature and pressure were 120 ° C, 140 ° C and 160 ° C. The laminate was obtained by heat sealing under conditions of 0.2 MPa and a sealing time of 1.0 second. The peel strength when the test substrate part was peeled from this laminate was measured. These results are also shown in Table 2.
[0052] [表 2] 実施例 1 1 実施例 1 2 比較例 1 原料 （重量部）  [0052] [Table 2] Example 1 1 Example 1 2 Comparative Example 1 Raw material (parts by weight)
E M A 8 5 8 5 8 5 E M A 8 5 8 5 8 5
S E B S 5 5 5 m P E - 2 1 0 1 0 1 0 防曇剤（ppm) 3 5 0 0 5 0 0 0 0 対ポ リ スチ レンシール強度 （N / 1 5 m m ) S E B S 5 5 5 m P E-2 1 0 1 0 1 0 Anti-fogging agent (ppm) 3 5 0 0 5 0 0 0 0 Anti-polystyrene seal strength (N / 15 mm)
1 2 0 °C 9 . 3 9 . 6 9 . 3 1 2 0 ° C 9.3 3 9.6 6 9.3
1 4 0 °C 1 1 . 0 1 0 . 6 1 6 . 21 4 0 ° C 1 1. 0 1 0. 6 1 6. 2
1 6 0 °C 1 4 . 0 1 4 . 5 1 5 . 4 防曇性 〇 〇 X [0053] [実施例 13〜14、比較例 2] 1 6 0 ° C 1 4. 0 1 4. 5 1 5. 4 Anti-fogging property ○ ○ X [0053] [Examples 13 to 14, Comparative Example 2]
表 3に示す配合組成のエチレン共重合体組成物を用いた以外は、実施例 11と同 様にして試験基材を作製し、その防曇性を評価した。またこの試験基材を用い、ポリ スチレンシートの代わりにポリプロピレンシートを用いた以外は実施例 11と同様にヒ ートシールして積層体を作製し、同様に剥離強度を測定した。結果を表 3に併記する  A test substrate was prepared in the same manner as in Example 11 except that the ethylene copolymer composition having the composition shown in Table 3 was used, and its antifogging property was evaluated. A laminate was prepared by heat sealing in the same manner as in Example 11 except that this test substrate was used and a polypropylene sheet was used instead of the polystyrene sheet, and the peel strength was measured in the same manner. The results are also shown in Table 3.
[0054] [表 3] [0054] [Table 3]
Figure imgf000018_0001
産業上の利用可能性
Figure imgf000018_0001
Industrial applicability
[0055] 本発明によれば、ポリプロピレンやポリスチレンなどの炭化水素系重合体に対して、 適度なヒートシール強度を有し、ヒートシール強度の温度依存性も少なぐ低温でヒ ートシールすることが可能な易開封性シール材料が提供される。  [0055] According to the present invention, it is possible to heat seal at a low temperature with moderate heat seal strength and less temperature dependence of heat seal strength for hydrocarbon polymers such as polypropylene and polystyrene. An easy-open seal material is provided.
[0056] 本発明によれば、また防曇性に優れ、ポリプロピレンやポリスチレンなどの炭化水素 系重合体に対して、適度なヒートシール強度を有し、ヒートシール強度の温度依存性 も少なく、低温でヒートシールすることが可能な易開封性シール材料が提供される。  [0056] According to the present invention, it has excellent anti-fogging properties, has an appropriate heat seal strength with respect to hydrocarbon polymers such as polypropylene and polystyrene, has little temperature dependency of the heat seal strength, and has a low temperature. An easily openable sealing material that can be heat-sealed is provided.
[0057] このような易開封性シール材料は、単層であるいは基材に積層して、炭化水素系 重合体に対する熱融着フィルムとして使用することができる。また基材に積層して、炭 化水素系重合体容器などの蓋材として使用することができる。とくに飲食品の包装材 料として使用するときに、防曇性が優れているので、冷蔵庫に保存された場合にも曇 りを生じることはなぐ商品イメージを損なうことはない。 [0057] Such an easy-open sealing material can be used as a heat-sealing film for a hydrocarbon polymer in a single layer or laminated on a base material. Laminate it on the base material, It can be used as a lid material for hydrogenated polymer containers and the like. In particular, when used as a packaging material for foods and drinks, it has excellent anti-fogging properties. Therefore, even if it is stored in a refrigerator, it does not spoil the product image.

Claims

請求の範囲 The scope of the claims
[I] エチレン.不飽和エステル共重合体 (A) 40〜98重量部、エラストマ一（B) 60〜0 重量部及び結晶性ポリオレフイン (C) 30〜0重量部（ただし (B)と (C)の合計量は 2 〜60重量部である）および (D)粘着付与剤 0〜30重量部 [ただし (A)、 (B)、（C)、（ D)の合計量は 100重量部]からなるエチレン共重合体組成物。  [I] Ethylene / unsaturated ester copolymer (A) 40 to 98 parts by weight, elastomer (B) 60 to 0 parts by weight and crystalline polyolefin (C) 30 to 0 parts by weight (However, (B) and (C ) Is 2 to 60 parts by weight) and (D) Tackifier 0 to 30 parts by weight [However, the total amount of (A), (B), (C) and (D) is 100 parts by weight] An ethylene copolymer composition comprising:
[2] 前記エチレン '不飽和エステル共重合体 (A)力 その不飽和エステル単位含有量 力^〜 30重量％であって、融点（T°C) (JIS K7121に準拠）と不飽和エステル単位 含有量 (Xモル％)が下記式を満足するエチレン '不飽和エステル共重合体 (A)であ る請求項 1に記載のエチレン共重合体組成物。  [2] The ethylene 'unsaturated ester copolymer (A) strength Unsaturated ester unit content power ^ ~ 30 wt%, melting point (T ° C) (based on JIS K7121) and unsaturated ester unit 2. The ethylene copolymer composition according to claim 1, wherein the content (X mol%) is an ethylene ′ unsaturated ester copolymer (A) satisfying the following formula.
3. 0X+ 125≥T≥— 3. 0X+ 109  3. 0X + 125≥T≥— 3. 0X + 109
[3] エチレン '不飽和エステル共重合体 (Α)力 エチレン 'アクリル酸メチル共重合体で ある請求項 1または 2に記載のエチレン共重合体組成物。  [3] The ethylene copolymer composition according to claim 1 or 2, wherein the ethylene 'unsaturated ester copolymer (エ ス テ ル) force is an ethylene' methyl acrylate copolymer.
[4] エラストマ一（Β)が、非晶性又は低結晶性のォレフィン共重合体及びスチレン系熱 可塑性エラストマ一力 選ばれるものである請求項 1〜3のいずれかに記載のェチレ ン共重合体組成物。  [4] The ethylene copolymer according to any one of claims 1 to 3, wherein the elastomer (Β) is selected from an amorphous or low crystalline olefin copolymer and a styrenic thermoplastic elastomer. Combined composition.
[5] 粘着付与榭脂 (D)が、水素添加炭化水素榭脂である請求項 1〜4のいずれかに記 載のエチレン共重合体組成物。  [5] The ethylene copolymer composition according to any one of [1] to [4], wherein the tackifier resin (D) is a hydrogenated hydrocarbon resin.
[6] 結晶性ポリオレフイン (C)が、ポリプロピレン又は直鎖低密度ポリエチレンである請 求項 1〜5のいずれかに記載のエチレン共重合体組成物。  [6] The ethylene copolymer composition according to any one of claims 1 to 5, wherein the crystalline polyolefin (C) is polypropylene or linear low-density polyethylene.
[7] 前記エチレン共重合体組成物が、さらにエチレン共重合体組成物中の重合体成分[7] The ethylene copolymer composition further comprises a polymer component in the ethylene copolymer composition.
100重量部に対し 10重量部までの防曇剤 (Ε)を配合する請求項 1〜6のいずれかに 記載のエチレン共重合体糸且成物。 The ethylene copolymer yarn and composite according to any one of claims 1 to 6, wherein 10 parts by weight of the antifogging agent (Ε) is blended with 100 parts by weight.
[8] 防曇剤が、多価アルコールのエステルである請求項 7に記載のエチレン共重合体 組成物。 [8] The ethylene copolymer composition according to [7], wherein the antifogging agent is an ester of a polyhydric alcohol.
[9] 請求項 1〜8のいずれかに記載のエチレン共重合体組成物からなる易開封性シー ル材料。  [9] An easily openable seal material comprising the ethylene copolymer composition according to any one of claims 1 to 8.
[10] 炭化水素系重合体にシールするための請求項 9記載の易開封性シール材料。  [10] The easily openable sealing material according to [9], for sealing to a hydrocarbon polymer.
[II] 基材に請求項 9または 10に記載の易開封性シール材料が積層されてなる包装材 [II] A packaging material in which the easy-open sealing material according to claim 9 or 10 is laminated on a base material
CTC0C/900Zdf/X3d 03 ZZ.060/900Z OAV CTC0C / 900Zdf / X3d 03 ZZ.060 / 900Z OAV
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