WO2022239728A1 - 相溶化剤、リサイクル助剤及び相溶化方法 - Google Patents
相溶化剤、リサイクル助剤及び相溶化方法 Download PDFInfo
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- WO2022239728A1 WO2022239728A1 PCT/JP2022/019647 JP2022019647W WO2022239728A1 WO 2022239728 A1 WO2022239728 A1 WO 2022239728A1 JP 2022019647 W JP2022019647 W JP 2022019647W WO 2022239728 A1 WO2022239728 A1 WO 2022239728A1
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- modified
- polymer
- copolymer
- ethylene copolymer
- modified ethylene
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- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UGDVGCADUVDYET-UHFFFAOYSA-N ethane-1,2-diamine;hexanedioic acid Chemical compound [NH3+]CC[NH3+].[O-]C(=O)CCCCC([O-])=O UGDVGCADUVDYET-UHFFFAOYSA-N 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical class C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JLSBBCYKZLAADL-UHFFFAOYSA-N n-benzylmethanimine Chemical compound C=NCC1=CC=CC=C1 JLSBBCYKZLAADL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000010816 packaging waste Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
- B29C39/20—Making multilayered or multicoloured articles
- B29C39/203—Making multilayered articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/003—Making articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0063—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to a compatibilizer and recycling aid using a modified ethylene copolymer.
- the present invention also relates to a compatibilization method using the modified ethylene copolymer.
- a recycling technique for the purpose of reducing the amount of plastic packaging waste, a recycling technique is known in which the following polymer composition is granulated/molded and recycled as a regrind layer or a recycled layer of a multilayer packaging material.
- EVOH ethylene-vinyl alcohol copolymer
- the ethylene/vinyl alcohol copolymer and the polyolefin in the polymer composition thus obtained are difficult to be compatible with each other.
- the ethylene-vinyl alcohol copolymer agglomerates in the regrind layer or the recycled layer, causing deterioration in transparency and mechanical strength, and affects the quality of the recycled multilayer packaging material. Therefore, the recyclability is poor when such recycling is repeated.
- Patent Documents 1 and 2 specifically describe a maleic anhydride-modified ethylene/octene copolymer as a maleic anhydride-modified ethylene copolymer.
- the transparency of the obtained polymer composition is improved by using the polymer composition containing the copolymer.
- the extrusion step of granulating/molding after melt-kneading the polymer composition there is a problem that foreign matter adheres (sometimes called "eyes") near the extrusion outlet (die head). there was a case. If foreign matter adheres to the vicinity of the extrusion outlet, the productivity deteriorates in order to remove the foreign matter.
- the present invention provides a polymer composition obtained by compatibilizing a polar polymer such as polyolefin and a barrier polar polymer such as ethylene-vinyl alcohol copolymer in an extrusion process without impairing the transparency.
- An object of the present invention is to provide a compatibilizer using a modified ethylene copolymer that can reduce the generation of foreign matter.
- the present invention is also useful in recycling offcuts generated in the manufacturing process of multi-layer packaging materials using non-polar polymers such as polyolefins and polar barrier polymers such as ethylene-vinyl alcohol copolymers.
- the present inventors have found that by using a specific modified ethylene copolymer as a compatibilizer, it is possible to reduce the generation of foreign matter during the extrusion process without impairing the transparency of the polymer composition. .
- the present inventors also found that by using a specific modified ethylene copolymer as a recycling aid in the recycling process, the generation of foreign matter in the extrusion process can be prevented without impairing the transparency of the polymer composition obtained by recycling. We have found that it can be reduced.
- the present inventors also found that a polar polymer and a non-polar polymer can be effectively compatibilized by using a specific modified ethylene copolymer.
- the present invention has the following features.
- a modified ethylene copolymer obtained by modifying a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms with an unsaturated carboxylic acid and/or its anhydride.
- a modified ethylene copolymer obtained by modifying a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms with an unsaturated carboxylic acid and/or its anhydride.
- a melt flow obtained by modifying a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms with an unsaturated carboxylic acid and/or its anhydride A compatibilization method for compatibilizing a polar polymer and a non-polar polymer in the presence of a modified ethylene copolymer having a rate (MFR: 190° C., 2.16 kg) of 15 to 39 g/10 min.
- a polymer composition obtained by compatibilizing a non-polar polymer such as polyolefin and a barrier polar polymer such as ethylene-vinyl alcohol copolymer obtained by compatibilizing a non-polar polymer such as polyolefin and a barrier polar polymer such as ethylene-vinyl alcohol copolymer. It is possible to reduce the generation of foreign matter in the extrusion process without impairing the transparency of the resin.
- the recycling aid of the present invention is generated in the manufacturing process of multilayer packaging materials using non-polar polymers such as polyolefins and polar barrier polymers such as ethylene-vinyl alcohol copolymer resins.
- non-polar polymers such as polyolefins
- polar barrier polymers such as ethylene-vinyl alcohol copolymer resins.
- the modified ethylene copolymer according to the present invention is used as a recycling aid for non-polar polymers such as polyolefins and barrier polar polymers such as ethylene-vinyl alcohol copolymers as recycled materials. Not limited. When one or both of a non-polar polymer and a polar polymer are virgin resins, the modified ethylene copolymer according to the present invention can also be effectively used as a compatibilizer for compatibilizing these polymers. can.
- the monomer units contained in the copolymer may be simply referred to as "units".
- a propylene-based monomer unit is referred to as a "propylene unit”
- an ethylene-based monomer unit and an ⁇ -olefin-based monomer unit are referred to as an "ethylene unit” and an “ ⁇ -olefin unit”, respectively.
- melt flow rate (MFR) of the polymer, the density, and the graft ratio of the modified polymer are values measured as follows.
- ⁇ MFR> MFR is measured under conditions of 190° C. and a load of 2.16 kg according to JIS K7210.
- Density is measured by a water substitution method according to JIS K7112.
- the graft ratio (also referred to as modified amount or graft amount) of a modified polymer such as a modified ethylene copolymer is the unsaturated carboxylic acid grafted to the raw material polymer described later when measured with an infrared spectrometer. and/or its anhydride (hereinafter sometimes referred to as "unsaturated carboxylic acid component") content.
- the graft ratio can also be obtained from a calibration curve prepared in advance by the method described above.
- the compatibilizer of the present invention is a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms with an unsaturated carboxylic acid and/or its anhydride. containing a modified modified ethylene copolymer (hereinafter sometimes referred to as "the modified ethylene copolymer of the present invention"), and the melt flow rate of the modified ethylene copolymer (MFR: 190°C, 2.16 kg); is 15 to 39 g/10 minutes.
- a compatibilizing agent has the effect of compatibilizing a non-polar material and a polar material and reducing the material dispersed particle size.
- a barrier polar polymer such as an ethylene/vinyl alcohol copolymer can be incorporated into a non-polar polymer such as polyolefin. can be finely dispersed in As a result, it is possible to improve the mechanical strength and transparency of a polymer composition or a recycled composition in which a polar barrier polymer such as an ethylene-vinyl alcohol copolymer is dispersed.
- the compatibilizer of the present invention is referred to as a recycling aid.
- scraps generated during the process of manufacturing multi-layer packaging materials using non-polar polymers such as polyolefin and polar barrier polymers such as ethylene-vinyl alcohol copolymer are collected.
- a non-polar polymer such as polyolefin and an ethylene-vinyl alcohol copolymer such as It is possible to compatibilize with a polar polymer having a good barrier property, and by granulation/molding, it is possible to suppress the deterioration of transparency and the generation of foreign matter, and to recycle it as a regrind layer of a multilayer packaging material.
- the compatibilizer or recycling aid containing the modified ethylene copolymer of the present invention as a main component, the ethylene-vinyl alcohol copolymer present in non-polar polymers such as polyolefins can be It becomes possible to reduce the dispersed particle size of the barrier polar polymer such as , and the effect of improving transparency and mechanical strength can be obtained.
- the low-molecular-weight component can be mixed into the regrind composition to exert a compatibilizing effect on the polar groups of the low-molecular-weight component generated in the extruder. As a result, it is possible to reduce the amount of low-molecular-weight components adhering as glue, and to reduce the amount of foreign matter adhering to the vicinity of the extrusion outlet.
- Non-polar polymers include polyolefins such as polypropylene-based polymers and polyethylene-based polymers.
- the compatibilizing agent of the present invention is preferably used particularly when compatibilizing a polyethylene polymer and a polar polymer.
- ⁇ -olefin monomers having 4 to 8 carbon atoms constituting the modified ethylene copolymer of the present invention include 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1- One or more of pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene and 1-octene can be used.
- ⁇ -olefin monomers having 4 to 6 carbon atoms are preferred, and ⁇ -olefin monomers having 4 carbon atoms, ie 1-butene, are particularly preferred.
- modified ethylene copolymers examples include modified ethylene/butene copolymers, modified ethylene/hexene copolymers, and modified ethylene/octene copolymers. Among these, from the viewpoint of recyclability, modified ethylene/butene copolymers and modified ethylene/hexene copolymers are preferable, and modified ethylene/butene copolymers are particularly preferable.
- the modified ethylene copolymer may contain monomer units other than the ethylene monomer and the above ⁇ -olefin monomer.
- the MFR (190°C, load 2.16 kg) of the modified ethylene copolymer of the present invention is 15 to 39 g/10 minutes.
- the density of the modified ethylene copolymer of the present invention is preferably 0.855-0.895 g/cm 3 . If the density of the modified ethylene copolymer is within the above range, the generation of foreign matter in the extrusion process can be reduced without impairing the transparency, the appearance of the recycled film can be maintained satisfactorily, and the mechanical properties are reduced. can also be prevented.
- the ethylene copolymer to be modified with the unsaturated carboxylic acid component is not particularly limited as long as the modified ethylene copolymer described above can be obtained, and known ethylene copolymers can be used.
- the MFR (190° C., load 2.16 kg) of the ethylene copolymer to be modified (hereinafter sometimes referred to as “raw polymer”) is not particularly limited, but is preferably 18 to 50 g/10 min. .
- the target modified ethylene copolymer tends to be easily obtained even if the change in MFR due to modification is taken into account.
- those having a density of 0.855 to 0.895 g/cm 3 can be preferably used.
- ethylene copolymer Only one type of ethylene copolymer may be used as the raw material polymer, or two or more types having different physical properties, compositions, etc. may be used in combination.
- Examples of unsaturated carboxylic acids that graft-modify ethylene copolymers include ⁇ , ⁇ -ethylenically unsaturated acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid and isocrotonic acid. Carboxylic acids are mentioned.
- Anhydrides of unsaturated carboxylic acids include 2-octen-1-yl succinate, 2-dodecen-1-yl succinate, 2-octadecen-1-yl succinate and maleic anhydride.
- unsaturated carboxylic acid components can be appropriately selected according to the ethylene copolymer to be modified and modification conditions.
- the unsaturated carboxylic acid components may be used singly or in combination of two or more.
- the unsaturated carboxylic acid component can also be used by dissolving it in an organic solvent or the like.
- the graft modification of the ethylene copolymer can be carried out by adding an unsaturated carboxylic acid component, preferably by graft-polymerizing the unsaturated carboxylic acid component to the ethylene copolymer in the presence of a radical generator.
- radical generators used here include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5 -bis(t-butyloxy)hexane, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxybenzoate, benzoyl peroxide, m-toluoyl peroxide, dicumyl peroxide, 1,3-bis( Organic and inorganic peroxides such as t-butylperoxyisopropyl)benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide; 2,2'-azobisisobutyronitrile, 2,2' -azobis(isobutyramide) dihalide, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
- the above-mentioned radical generator can be appropriately selected according to the type of ethylene copolymer to be subjected to the modification reaction, the type of unsaturated carboxylic acid component as the modifier, and the modification conditions.
- One type of radical generator may be used alone, or two or more types may be used in combination.
- the radical generator can also be used by dissolving it in an organic solvent or the like.
- modification reaction for obtaining the modified ethylene copolymer of the present invention
- various known reaction methods such as melt-kneading reaction method, solution reaction method, and suspension dispersion reaction method can be used.
- a melt-kneading reaction method is usually preferred.
- melt-kneading reaction method When the melt-kneading reaction method is used, the above components may be uniformly mixed at a predetermined compounding ratio and then melt-kneaded.
- a Henschel mixer, a ribbon blender, a V-type blender, or the like is used for mixing.
- a Banbury mixer, a kneader, a roll, a multi-screw kneading extruder such as a single-screw or a twin-screw, or the like is used.
- Melt-kneading is usually carried out at 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and usually 300°C or lower, preferably 280°C or lower, more preferably 250°C or lower so that the polymer does not thermally deteriorate. do it in range.
- the blending amount of the unsaturated carboxylic acid component as a modifier is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0 parts by mass with respect to 100 parts by mass of the ethylene copolymer as the raw material polymer. .1 parts by mass or more and usually 30 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less.
- the blending amount of the radical generator is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the ethylene copolymer as the raw material polymer. , usually 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 part by mass or less.
- Sufficient modification can be achieved by setting the blending amount of the radical generator to the above lower limit or more.
- the amount of the radical generator By setting the amount of the radical generator to be equal to or less than the above upper limit, the increase in the molecular weight (viscosity increase) during modification of the ethylene copolymer can be suppressed within a desired range, and the desired modified ethylene copolymer can be easily obtained. There is a tendency.
- a graft polymerization reaction in which an unsaturated carboxylic acid component is added to the ethylene copolymer mainly occurs, but a cross-linking reaction also occurs. Due to this cross-linking, the resulting modified product tends to have an increased molecular weight and a higher melt viscosity. Therefore, if the amount of the radical generator used is too large, the graft polymerization reaction tends to occur, but at the same time, the cross-linking reaction that leads to the increase in the melt viscosity also tends to occur, which is not preferable.
- the graft ratio of the modified ethylene copolymer of the present invention is preferably 0.1 to 1.0% by mass, more preferably 0.6 to 1.0% by mass, and more preferably 0.8 to 1.0%. % by mass is more preferred.
- Favorable recyclability can be obtained as a graft rate is more than the said minimum. If the grafting ratio is too high, burns and the like increase, and as a result, the appearance of the recycled film is adversely affected. Therefore, the graft ratio of the modified ethylene copolymer is preferably not more than the above upper limit.
- Modified ethylene copolymer composition When the modified ethylene copolymer of the present invention is used as a compatibilizer or the like, other optional additives, polymers, etc. (hereinafter referred to as "other components ”) can be used as a modified ethylene copolymer composition.
- the other components may be used alone or in combination of two or more in any combination and ratio.
- additives include heat stabilizers and antioxidants, and hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides can be used.
- a mixing method for producing a modified ethylene copolymer composition using a modified ethylene copolymer and optionally added other components as the compatibilizer or recycling aid of the present invention is practical.
- a melt-kneading method is preferred.
- Other components may be added to the ethylene copolymer before modification, and the aforementioned graft modification may be performed together with the mixing of the other components.
- Other components may be mixed with the modified ethylene copolymer after graft modification.
- the modified ethylene copolymer or ethylene copolymer of the present invention and other components that are added as necessary are mixed at a predetermined mixing ratio in a Henschel mixer, a ribbon A method of mixing uniformly using a blender, V-type blender, etc., and then kneading using a multi-screw kneading extruder, for example, a twin-screw kneading extruder TEX25 of Japan Steel Works, Ltd. can be exemplified.
- the temperature for melt-kneading each component is generally 100 to 300°C, preferably 120 to 280°C, more preferably 150 to 250°C, like the temperature for graft modification described above.
- the kneading order and method of each component are not particularly limited.
- a method of collectively kneading the modified ethylene copolymer or ethylene copolymer of the present invention and optionally other components, or the modified ethylene copolymer or ethylene copolymer of the present invention and optionally A part of the other ingredients used in the method may be kneaded in advance, and then kneaded with the remaining ingredients.
- the compatibilization method of the present invention uses the modified ethylene copolymer of the present invention described above, that is, a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms. in the presence of a modified ethylene copolymer modified with an unsaturated carboxylic acid and/or its anhydride and having a melt flow rate (MFR: 190° C., 2.16 kg) of 15 to 39 g/10 min. It is a compatibilization method for compatibilizing the coalescence and the non-polar polymer.
- MFR melt flow rate
- non-polar polymers examples include polyolefin polymers (a) such as polypropylene polymers and polyethylene polymers, which will be described later.
- the effects of the present invention are particularly effective when compatibilizing a polyethylene polymer and a polar polymer.
- the polar polymer includes a polar polymer (b) described later, preferably a barrier polymer such as an ethylene-vinyl alcohol copolymer.
- the amount ratio of the polar polymer and the non-polar polymer can be compatibilized.
- these can be compatibilized in a wide range of 1 to 50 parts by weight of the polar polymer per 100 parts by weight of the non-polar polymer.
- the amount of the modified ethylene copolymer used there is no particular limitation on the amount of the modified ethylene copolymer used. As an embodiment, it is preferably 0.1 to 25 parts by weight, particularly 0.5 to 15 parts by weight, and most preferably 1 to 10 parts by weight with respect to 100 parts by weight of the nonpolar polymer. When the amount of the modified ethylene copolymer used is at least the above lower limit, a sufficient compatibilizing effect by the modified ethylene copolymer can be obtained. When the amount of the modified ethylene copolymer used is equal to or less than the above upper limit, overreaction between the polar polymer and the modified ethylene copolymer tends to be suppressed.
- the modified ethylene copolymer may be used as the modified ethylene copolymer composition described above.
- components other than the modified ethylene copolymer, the polar polymer and the non-polar polymer may be present in the compatibilization system.
- the polymer composition of the present invention contains an ethylene/vinyl alcohol copolymer (b1) (hereinafter sometimes referred to as "EVOH (b1)”) and A polymer composition containing 0.1 to 20 parts by mass of at least one polar polymer (b) selected from polyamide polymers (b2) and 0.1 to 25 parts by mass of an acid-modified polyolefin (d). is preferred.
- EVOH ethylene/vinyl alcohol copolymer
- a polymer composition containing 0.1 to 20 parts by mass of at least one polar polymer (b) selected from polyamide polymers (b2) and 0.1 to 25 parts by mass of an acid-modified polyolefin (d). is preferred.
- the acid-modified polyolefin (d) is a copolymer of an ethylene monomer and one or more ⁇ -olefin monomers having 4 to 8 carbon atoms, an unsaturated carboxylic acid and/or
- the modified ethylene copolymer of the present invention is modified with an anhydride and has a melt flow rate (MFR: 190° C., 2.16 kg) of 15 to 39 g/10 min.
- the polymer composition of the present invention may further contain an acid-modified polyolefin (c) having a melt flow rate different from that of the acid-modified polyolefin (d), if necessary.
- an acid-modified polyolefin (c) having a melt flow rate different from that of the acid-modified polyolefin (d), if necessary.
- Polyolefin-based polymer (a) includes polypropylene; propylene-based copolymer obtained by copolymerizing propylene with ⁇ -olefin such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene; low density Polyethylene such as polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; Ethylene-based copolymers of ethylene and ⁇ -olefins such as 1-butene, 1-hexene, and 4-methyl-1-pentene Copolymer; poly(1-butene), poly(4-methyl-1-pentene) and the like.
- ⁇ -olefin such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene
- low density Polyethylene such as polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene
- the polyolefin-based polymer (a) may be used singly, or two or more of which differ in copolymer component composition, physical properties, etc., may be mixed and used.
- the polyolefin polymer (a) propylene-based polymers such as polypropylene and propylene-based copolymers, and ethylene-based polymers such as polyethylene and ethylene-based copolymers are preferable.
- the polyolefin polymer (a) is preferably a propylene polymer, and more preferably polypropylene.
- the polyolefin polymer (a) is preferably an ethylene polymer, more preferably polyethylene, and still more preferably high-density polyethylene.
- the melt flow rate (MFR: 190° C. or 210° C., 2.16 kg) of the polyolefin polymer (a) is preferably 0.01 to 10 g/10 minutes. If the MFR of the polyolefin polymer (a) is 0.01 g/10 minutes or more, the difference in melt viscosity between the polar polymer (b) and the polyolefin polymer (a) does not become too large, and the polymer composition The dispersibility of the polar polymer (b) in the resin becomes good, and the impact resistance of the resulting molded article is excellent. If the MFR of the polyolefin polymer (a) is 10 g/10 minutes or less, the impact resistance of the resulting molded article will be good.
- the MFR of the polyolefin polymer (a) is more preferably 5 g/10 minutes or less, still more preferably 3 g/10 minutes or less, and particularly preferably 2 g/10 minutes or less.
- the MFR of the polyolefin-based polymer (a) is obtained by weighting and averaging the MFRs of the respective polymers by the mixture mass ratio.
- the EVOH (b1), the polyamide polymer (b2), the acid-modified polyolefin (c), and the acid-modified polyolefin (d) described below are a mixture of a plurality of types of polymers, the same is true for the polyolefin polymer (a). to find the MFR of each.
- the polar polymer (b) is at least one barrier polar polymer selected from EVOH (b1) and polyamide polymer (b2).
- the polar polymer (b) may be a mixture of one or more EVOH (b1) and one or more polyamide polymer (b2).
- the mixing ratio is not particularly limited.
- EVOH (b1) can be obtained by saponifying an ethylene-vinyl ester copolymer.
- Vinyl esters include vinyl acetate as a typical vinyl ester, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used.
- the ethylene/vinyl ester copolymer is produced by any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, and the like. Saponification of the ethylene-vinyl ester copolymer can also be performed by a known method.
- the ethylene unit content of EVOH (b1) is a value measured based on ISO14663, and is preferably 20 to 60 mol%. When the ethylene unit content is 20 mol % or more, the EVOH (b1) in the polymer composition has good gas barrier properties and melt moldability at high humidity.
- the ethylene unit content of EVOH (b1) is more preferably 23 mol % or more. If the ethylene unit content is 60 mol % or less, the barrier properties are excellent.
- the ethylene unit content of EVOH (b1) is more preferably 55 mol% or less, still more preferably 50 mol% or less, and particularly preferably less than 50 mol%.
- the degree of saponification of the vinyl ester unit of EVOH (b1) is a value measured based on JIS K6726 (however, EVOH is a solution uniformly dissolved in a water/methanol solvent), and has barrier properties, thermal stability, and moisture resistance. 80 mol% or more is preferable, 98 mol% or more is more preferable, and 99 mol% or more is still more preferable from the viewpoint of the property.
- the melt flow rate (MFR: 210°C, 2.16 kg) of EVOH (b1) is preferably 0.1 to 100 g/10 minutes.
- MFR of EVOH (b1) is 100 g/10 minutes or less, the difference in melt viscosity between EVOH (b1) and acid-modified polyolefin (c) does not become too large, and EVOH (b1) is dispersed in the polymer composition. and excellent thermal stability.
- the MFR of EVOH (b1) is more preferably 50 g/10 minutes or less, still more preferably 30 g/10 minutes or less.
- the MFR of the EVOH (b1) is 0.1 g/10 minutes or more, the difference in viscosity from the acid-modified polyolefin (d) does not become too large, and the dispersibility of the EVOH (b1) in the polymer composition becomes good. , good impact resistance.
- the MFR of EVOH (b1) is more preferably 0.5 g/10 minutes or more.
- EVOH (b1) may be copolymerized with a polymerizable monomer other than ethylene and vinyl ester within a range that does not impair the effects of the present invention, generally within a range of 5 mol% or less.
- polymerizable monomers include ⁇ -olefins such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene; - hydroxy group-containing ⁇ -olefins such as butene-1,2-diol, esters thereof, hydroxy group-containing ⁇ -olefin derivatives such as acylated products; Hydroxymethylvinylidene diacetates such as propionyloxy-2-methylenepropane and 1,3-dibutyronyloxy-2-methylenepropane; unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides
- EVOH (b1) it is also possible to use "post-modified" EVOH such as urethanization, acetalization, cyanoethylation, and oxyalkylenation.
- EVOH (b1) Only one type of EVOH (b1) may be used, or two or more types having different vinyl ester types, ethylene unit contents, physical properties, etc. may be used in combination.
- Polyamide polymer (b2) A well-known thing can be used as a polyamide-type polymer (b2). Specifically, polycapramide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryllactam (nylon 12), etc. homopolymer of.
- polyamide-based copolymers include polyethylenediamineadipamide (nylon 26), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), and polyhexamethylenesebacamide (nylon 610).
- polyhexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam/lauryllactam copolymer (nylon 6/12), caprolactam/ ⁇ - aminononanoic acid copolymer (nylon 6/9), caprolactam/hexamethylenediammonium adipate copolymer (nylon 6/66), lauryllactam/hexamethylenediammonium adipate copolymer (nylon 12/66), ethylenediamine adipate Pamide/Hexamethylenediammonium Adipate Copolymer (Nylon 26/66), Caprolactam/Hexamethylenediammonium Adipate/Hexamethylenediammonium Sebacate Copolymer (Nylon 66/610), Ethylene Ammonium Adipate/Hexamethylenediammonium Aliphatic poly
- the melt flow rate (MFR: 210°C, 2.16 kg) of the polyamide polymer (b2) is preferably 0.1 to 30 g/10 minutes.
- MFR of the polyamide-based polymer (b2) is within the above range, it is possible to optimally react with the acid-modified polyolefin (d) as a compatibilizer and improve dispersibility.
- polyamide polymer (b2) Only one type of polyamide polymer (b2) may be used, or two or more types having different copolymer compositions, physical properties, etc. may be mixed and used.
- the acid-modified polyolefin (c) include graft-modified polyolefins obtained by graft-modifying polyolefins with acids, and olefin-based copolymers obtained by copolymerizing olefins and acids. These may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, as the acid-modified polyolefin (c), a modified polyolefin modified with an unsaturated carboxylic acid and/or a derivative thereof is preferable.
- the acid-modified polyolefin (c) is preferably the same type of polyolefin polymer as the polyolefin polymer (a) acid-modified.
- the acid-modified polyolefin (c) is preferably acid-modified polypropylene.
- the acid-modified polyolefin (c) is preferably acid-modified polyethylene.
- Examples of unsaturated carboxylic acids used for graft modification of the acid-modified polyolefin (c) include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and maleic acid.
- Derivatives of unsaturated carboxylic acids include acid anhydrides such as maleic anhydride and itaconic anhydride. Of these, maleic anhydride is most preferred.
- the melt flow rate (MFR: 190°C, 2.16 kg) of the acid-modified polyolefin (c) is 0.01 g/10 min or more and less than 15 g/10 min, preferably 0.5 to 10 g/10 min.
- MFR of the acid-modified polyolefin (c) is within the above range, the viscosity of the acid-modified polyolefin (c), the polyolefin polymer (a) and the acid-modified polyolefin (d) are well balanced. As a result, the dispersibility of the polar polymer (b) is improved, and the impact resistance of the molded product is improved.
- the density of the acid-modified polyolefin (c) is preferably 0.855 to 0.955 g/cm 3 . If the density of the acid-modified polyolefin (c) is within the above range, the generation of foreign matter in the extrusion process can be reduced without impairing the transparency, the appearance of the recycled film can be maintained well, and the mechanical properties can be improved. decline can be prevented.
- the amount of unsaturated carboxylic acid and/or derivative thereof contained in the acid-modified polyolefin (c) is preferably 0.001 to 3% by mass of the acid-modified polyolefin (c). If the unsaturated carboxylic acid and/or its derivative amount is within the above range, the dispersibility of the polar polymer (b) in the polymer composition of the present invention is improved, resulting in moldability. improves.
- Only one kind of acid-modified polyolefin (c) may be used, or two or more kinds of polymers having different types and physical properties before modification may be mixed and used.
- the polymer composition of the present invention contains 0.1 to 20 parts by mass of the polar polymer (b) and 0.1 to 25 parts by mass of the acid-modified polyolefin (d) with respect to 100 parts by mass of the polyolefin polymer (a). It is preferable to contain a part.
- the polar polymer (b) is contained in an amount of 1 to 15 parts by mass, more preferably 5 to 10 parts by mass based on 100 parts by mass of the polyolefin polymer (a).
- the acid-modified polyolefin (d) is less than 0.1 parts by mass, the effect of finely dispersing the polar polymer (b) in the polymer composition cannot be sufficiently obtained, and the recycled composition has reduced transparency. It is not possible to sufficiently prevent the generation of foreign matter in the extrusion process. If the acid-modified polyolefin (d) exceeds 25 parts by mass, it is not possible to sufficiently prevent the generation of foreign matter during the extrusion process.
- the acid-modified polyolefin (d) is more preferably contained in an amount of 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass based on 100 parts by mass of the polyolefin polymer (a).
- the content of the acid-modified polyolefin (c) is 0.1 to 20 parts per 100 parts by mass of the polyolefin copolymer (a). It is preferably contained in parts by mass, particularly 1 to 18 parts by mass, especially 5 to 15 parts by mass. If the content of the acid-modified polyolefin (c) is within the above range, the dispersibility of the polar polymer (b) in the polymer composition will be better, and the impact resistance of the resulting molded article will be enhanced.
- the polymer composition of the present invention may contain a polyolefin polymer (a), a polar polymer (b), an acid-modified polyolefin (c), an acid-modified Polymers other than the polyolefin (d), optional additives, etc. (hereinafter referred to as "other components") can be blended.
- the other components may be used alone or in combination of two or more in any combination and ratio.
- additives examples include antioxidants, UV absorbers, plasticizers, lubricants, fillers, and antistatic agents.
- the total content of these additives in the polymer composition of the present invention is usually 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.
- the method for mixing each component for obtaining the polymer composition of the present invention is not particularly limited, and examples thereof include the following methods.
- the polyolefin polymer (a), the polar polymer (b), the acid-modified polyolefin (d), the acid-modified polyolefin (c) used as necessary, and some of the other components are previously melt-kneaded, A method of blending and melt-kneading other components;
- a recovered multilayer packaging material containing the polyolefin polymer (a) layer and the polar polymer (b) layer, or the polyolefin polymer (a) layer and the polar polymer
- a preferred method is to melt-knead a recovered multilayer packaging material containing the (b) layer and the acid-modified polyolefin (c) layer and a compatibilizer containing the acid-modified polyolefin (d).
- the recovered multilayer packaging material is scrap such as burrs generated when manufacturing a molded product made of the multilayer packaging material, and recovered products such as unacceptable products at the time of molding.
- compatibilizers Additives blended when such a recovered material is melt-kneaded are called compatibilizers, and here, compatibilizers containing acid-modified polyolefin (d) are used.
- the content of the acid-modified polyolefin (d) in the compatibilizer is preferably 5-100% by mass.
- the content of the acid-modified polyolefin (d) is more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 50% by mass or more.
- each component is uniformly mixed at a predetermined mixing ratio using a Henschel mixer, a ribbon blender, a V-type blender, etc., and then a multi-screw kneading extruder, such as a Japanese A method of kneading using TEX25, which is a twin-screw kneading extruder in a steel mill, can be exemplified.
- the temperature for melt-kneading each component is usually 100 to 300°C, preferably 120 to 280°C, more preferably 150 to 250°C, similar to the temperature during graft modification of the acid-modified polyolefin (d) described above.
- molded article of the present invention By molding the polymer composition of the present invention, a molded article (hereinafter sometimes referred to as "the molded article of the present invention") can be obtained.
- Examples of the shape of the molded article of the present invention include films, sheets, tapes, cups, trays, tubes, bottles, pipes, filaments, extrudates with irregular cross-sections, and various irregular shaped articles.
- the method for molding the polymer composition of the present invention is not particularly limited, and any molding method applicable to general polymer compositions can be applied. Examples include extrusion molding, blow molding, injection molding, and thermoforming.
- the heat stretching process means that a film, sheet, or parison-shaped molded product that has been uniformly heated thermally is subjected to cups, trays, tubes, bottles, and films by chucking, plugging, vacuum force, pneumatic force, blowing, or the like. It means the operation of shaping uniformly into a shape.
- stretching methods include roll stretching, tenter stretching, tubular stretching, stretch blowing, vacuum forming, pressure forming, and vacuum pressure forming. Stretching may be either uniaxial stretching or biaxial stretching. In the case of biaxial stretching, either a simultaneous biaxial stretching system or a sequential biaxial stretching system can be employed.
- the stretching temperature is usually 60 to 170°C, preferably 80 to 160°C.
- the raw materials used in the preparation of the modified copolymer and the regrind composition in the following examples and comparative examples are as follows.
- EVOH Soarnol (registered trademark) DC3203RB manufactured by Mitsubishi Chemical Corporation (MFR (210°C, load 2.16 kg): 3.8 g/10 minutes, density: 1.19 g/cm 3 , ethylene unit content: 32 mol%, Saponification degree: 99.9 mol%)
- Adhesive polymer Modic (registered trademark) M512 manufactured by Mitsubishi Chemical Corporation (MFR (190°C, load 2.16 kg): 1.0 g/10 minutes, density: 0.900 g/cm 3 )
- Example 2 to 4 Comparative Examples 1 to 5> 1-pass and 2-pass regrind compositions were obtained in the same manner as in Example 1, except that the composition was changed as shown in Table-2. The obtained regrind composition was evaluated for the following (1) to (4). The evaluation results are shown in Table-2.
- the internal HAZE is an index for evaluating the dispersibility of EVOH in polyethylene, and the smaller the internal HAZE value, the finer the EVOH dispersed and the better the appearance. In this evaluation, when the internal HAZE value is 17% or less, the dispersibility of EVOH is evaluated as good.
- Examples 1 to 4 using the modified ethylene copolymer of the present invention could eliminate or reduce the amount of adhered foreign matter without impairing transparency. In addition, excellent results were obtained in terms of internal HAZE, mechanical properties, and recyclability.
- Comparative Example 1 using a modified ethylene-butene copolymer (A'-2) with an MFR of 2 g/10 minutes a modified ethylene-butene copolymer (A'-2) with an MFR of 13 g/10 minutes Comparative Example 2 using 3) and Comparative Example 3 using the modified ethylene-butene copolymer (A'-4) having an MFR of 59 g/10 min resulted in a large amount of foreign matter adhered.
- Comparative Example 4 using a modified ethylene/octene copolymer (D'-1) having an MFR of 640 g/10 min has a high internal HAZE in film evaluation using a regrind composition after 2 passes, and is inferior in recyclability. result.
- Comparative Example 5 shows an example in which no compatibilizing agent is used, and the results show that the internal HAZE, the tensile strength at break, and the amount of adhered foreign matter all deteriorate significantly in the 2-pass extrusion process. That is, it is difficult to recycle a regrind composition comprising polyethylene, EVOH, and an adhesive resin polymer.
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Abstract
Description
ポリオレフィンのような非極性の重合体とエチレン・ビニルアルコール共重合体(EVOH)のようなバリア性の極性の重合体とを用いた多層包材を製造する際の工程中に発生する端材や製造された多層包材を回収し、粉砕等により微細化したものを溶融混練した重合体組成物。
しかし、一方で、該重合体組成物を溶融混練した後の造粒/成形する押出工程で、押出出口(ダイスヘッド)付近に異物が付着(「めやに」と呼ばれることもある)する問題が発生する場合があった。押出出口付近に異物が付着すると、これを除去するために生産性が悪化する。また、異物が造粒/成形後の重合体組成物に含有されることで造粒品/成形品の品質が低下する場合もある。また、多層包材のリグラインド層またはリサイクル層として再利用を繰り返した場合、ポリオレフィンの種類によってはリサイクル性が悪化する問題があった。
本発明はまた、ポリオレフィン等の非極性の重合体とエチレン・ビニルアルコール共重合体等のバリア性の極性の重合体とを用いた多層包材の製造工程で発生する端材をリサイクルする際に得られる重合体組成物の透明性を損なうことなく、押出工程での異物の発生の低減を可能とする変性エチレン共重合体を用いたリサイクル助剤を提供することを目的とする。
本発明はまた、このような変性エチレン共重合体を用いた相溶化方法を提供することを目的とする。
本発明者らはまた、リサイクル工程に特定の変性エチレン共重合体をリサイクル助剤として用いることで、リサイクルにより得られる重合体組成物の透明性を損なうことなく、押出工程での異物の発生を低減することができることを見出した。
本発明者らはまた、特定の変性エチレン共重合体を用いることで、極性の重合体と非極性の重合体とを効果的に相溶化することができることを見出した。
本明細書において、「~」を用いてその前後に数値又は物性値を挟んで表現する場合、その前後の値を含むものとして用いることする。
MFRは、JIS K7210に従い、190℃、荷重2.16kgの条件で測定される。
密度は、JIS K7112に従い、水中置換法で測定される。
変性エチレン共重合体等の変性重合体のグラフト率(変性量、グラフト量とも称される。)は、赤外分光測定装置で測定した際の、後述の原料重合体にグラフトした不飽和カルボン酸及び/又はその無水物(以下、「不飽和カルボン酸成分」と称す場合がある。)の含有率を意味する。
不飽和カルボン酸成分の含有率は、例えば、変性重合体を厚さ100μm程度のシート状にプレス成形したサンプル中の不飽和カルボン酸成分特有の吸収、具体的には1,900~1,600cm-1(C=O伸縮振動帯)のカルボニル特性吸収を測定することにより求めることができる。
グラフト率は、上記の方法で、予め作成した検量線から求めることもできる。
本発明の相溶化剤は、エチレン単量体と炭素数4~8のα-オレフィン単量体の1種又は2種以上との共重合体を、不飽和カルボン酸及び/又はその無水物により変性した変性エチレン共重合体(以下、「本発明の変性エチレン共重合体」と称す場合がある。)を含み、当該変性エチレン共重合体のメルトフローレート(MFR:190℃、2.16kg)が15~39g/10分であることを特徴とする。
本発明では、不飽和カルボン酸成分によりグラフト変性された変性エチレン共重合体を用いることで、エチレン・ビニルアルコール共重合体等のバリア性の極性の重合体をポリオレフィン等の非極性の重合体中に微細に分散させることができる。その結果、エチレン・ビニルアルコール共重合体等のバリア性の極性の重合体が分散した重合体組成物やリサイクル組成物において、機械強度や透明性を向上させることができる。
例えば、ポリオレフィンのような非極性の重合体とエチレン・ビニルアルコール共重合体のようなバリア性の極性の重合体とを用いた多層包材を製造する際の工程中に発生する端材を回収し、粉砕等により微細化したものを、本発明の相溶化剤をリサイクル助剤として用いて、溶融混練することで、ポリオレフィンのような非極性の重合体とエチレン・ビニルアルコール共重合体のようなバリア性の極性の重合体とを相溶化させ、造粒/成形により、透明性の低下、異物発生を抑制して多層包材のリグラインド層として再生利用することができる。
本発明の変性エチレン共重合体を構成する炭素数4~8のα-オレフィン単量体としては、例えば、1-ブテン、3-メチル-1-ブテン、1-ペンテン、4-メチル-1-ペンテン、4,4-ジメチル-1-ペンテン、1-ヘキセン、4-メチル-1-ヘキセン、1-ヘプテン、1-オクテンの1種又は2種以上が挙げられる。これらの中でも、炭素数4~6のα-オレフィン単量体が好ましく、炭素数4のα-オレフィン単量体、即ち、1-ブテンが特に好ましい。
不飽和カルボン酸成分による変性に供するエチレン共重合体としては、上述の変性エチレン共重合体が得られれば、特に限定されず、公知のエチレン共重合体を使用することができる。
エチレン共重合体をグラフト変性する不飽和カルボン酸としては、例えば、アクリル酸、マレイン酸、フマル酸、テトラヒドロフマル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸といったα,β-エチレン性不飽和カルボン酸が挙げられる。不飽和カルボン酸の無水物としては、コハク酸2-オクテン-1-イル無水物、コハク酸2-ドデセン-1-イル無水物、コハク酸2-オクタデセン-1-イル無水物、マレイン酸無水物、2,3-ジメチルマレイン酸無水物、ブロモマレイン酸無水物、ジクロロマレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、1-ブテン-3,4-ジカルボン酸無水物、1-シクロペンテン-1,2-ジカルボン酸無水物、1,2,3,6-テトラヒドロフタル酸無水物、3,4,5,6-テトラヒドロフタル酸無水物、exo-3,6-エポキシ-1,2,3,6-テトラヒドロフタル酸無水物、5-ノルボルネン-2,3-ジカルボン酸無水物、メチル-5-ノルボルネン-2,3-ジカルボン酸無水物、endo-ビシクロ[2.2.2]オクト-5-エン-2,3-ジカルボン酸無水物、ビシクロ[2.2.2]オクト-7-エン-2,3,5,6-テトラカルボン酸無水物等の不飽和カルボン酸無水物が挙げられる。
不飽和カルボン酸成分は、有機溶剤などに溶解して使用することもできる。
ラジカル発生剤は有機溶剤などに溶解して使用することもできる。
本発明の変性エチレン共重合体のグラフト率は0.1~1.0質量%であることが好ましく、0.6~1.0質量%であることがより好ましく、0.8~1.0質量%であることが更に好ましい。グラフト率が上記下限以上であると、良好なリサイクル性を得ることができる。グラフト率が高過ぎると焼け等が多くなり、その結果、リサイクルフィルムの外観等に悪影響を及ぼす。このため、変性エチレン共重合体のグラフト率は上記上限以下であることが好ましい。
本発明の変性エチレン共重合体を相溶化剤等として用いる場合、本発明の効果を著しく損なわない範囲で各種目的に応じ他の任意の添加剤や重合体等(以下、これらを「その他の成分」と称す。)を配合した変性エチレン共重合体組成物として用いることもできる。
その他の成分は、1種類のみを用いても、2種類以上を任意の組合せと比率で併用してもよい。
各成分の混練順序及び方法は、特に限定されるものではない。本発明の変性エチレン共重合体又はエチレン共重合体と必要に応じて用いられるその他の成分とを一括して混練する方法、又は本発明の変性エチレン共重合体又はエチレン共重合体と必要に応じて用いられるその他の成分の一部を予め混練しておき、その後残りの成分を混練する方法、のいずれでもよい。
本発明の相溶化方法は、上述の本発明の変性エチレン共重合体、即ち、エチレン単量体と炭素数4~8のα-オレフィン単量体の1種又は2種以上との共重合体を、不飽和カルボン酸及び/又はその無水物により変性した、メルトフローレート(MFR:190℃、2.16kg)が15~39g/10分の変性エチレン共重合体の存在下で、極性の重合体と非極性の重合体とを相溶化する相溶化方法である。
極性の重合体としては、後述の極性重合体(b)、好ましくはエチレン・ビニルアルコール共重合体のようなバリア性の重合体が挙げられる。
本発明の相溶化方法において、相溶化系内には、変性エチレン共重合体、極性の重合体及び非極性の重合体以外の他の成分が存在していてもよい。
本発明の変性エチレン共重合体を用いて、リサイクル性に優れた重合体組成物(以下、「本発明の重合体組成物」と称す場合がある。)を得ることができる。
本発明の重合体組成物は、ポリオレフィン系重合体(a)100質量部に対し、エチレン・ビニルアルコール系共重合体(b1)(以下、「EVOH(b1)」と称す場合がある。)及びポリアミド系重合体(b2)から選ばれる少なくとも1つの極性重合体(b)を0.1~20質量部、酸変性ポリオレフィン(d)を0.1~25質量部含有する重合体組成物であることが好ましい。
ポリオレフィン系重合体(a)としては、ポリプロピレン;プロピレンと、エチレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテンなどのα-オレフィンとを共重合したプロピレン系共重合体;低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレンなどのポリエチレン;エチレンと、1-ブテン、1-ヘキセン、4-メチル-1-ペンテンなどのα-オレフィンとを共重合したエチレン系共重合体;ポリ(1-ブテン)、ポリ(4-メチル-1-ペンテン)などが挙げられる。
耐熱性に優れた成形品が得られる観点からは、ポリオレフィン系重合体(a)として、プロピレン系重合体が好ましく、ポリプロピレンがより好ましい。
透明性に優れた成形品が得られる観点からは、ポリオレフィン系重合体(a)として、エチレン系重合体が好ましく、ポリエチレンがより好ましく、高密度ポリエチレンが更に好ましい。
ポリオレフィン系重合体(a)が複数種類の重合体の混合物である場合、それぞれの重合体のMFRを混合質量比で加重平均した値をポリオレフィン系重合体(a)のMFRとする。
後述のEVOH(b1)、ポリアミド系重合体(b2)、酸変性ポリオレフィン(c)、酸変性ポリオレフィン(d)が複数種類の重合体の混合物である場合も、ポリオレフィン系重合体(a)と同様にして、それぞれのMFRを求める。
極性重合体(b)は、EVOH(b1)及びポリアミド系重合体(b2)から選ばれる少なくとも一つのバリア性極性重合体である。
極性重合体(b)は、EVOH(b1)の1種又は2種以上とポリアミド系重合体(b2)の1種又は2種以上を混合して用いてもよい。EVOH(b1)とポリアミド系重合体(b2)を混合して用いる場合、その混合割合には特に制限はない。
EVOH(b1)は、エチレン・ビニルエステル共重合体をけん化することにより得ることができる。ビニルエステルとしては酢酸ビニルが代表的なものとして挙げられるが、その他の脂肪酸ビニルエステル(プロピオン酸ビニル、ピバリン酸ビニルなど)も使用できる。エチレン・ビニルエステル共重合体は、公知の任意の重合法、例えば、溶液重合、懸濁重合、エマルジョン重合等により製造される。エチレン・ビニルエステル共重合体のケン化も、公知の方法で行い得る。
ポリアミド系重合体(b2)としては、公知のものを用いることができる。
具体的には、ポリカプラミド(ナイロン6)、ポリ-ω-アミノヘプタン酸(ナイロン7)、ポリ-ω-アミノノナン酸(ナイロン9)、ポリウンデカンアミド(ナイロン11)、ポリラウリルラクタム(ナイロン12)等のホモポリマーが挙げられる。
ポリアミド系共重合体としては、ポリエチレンジアミンアジパミド(ナイロン26)、ポリテトラメチレンアジパミド(ナイロン46)、ポリヘキサメチレンアジパミド(ナイロン66)、ポリヘキサメチレンセバカミド(ナイロン610)、ポリヘキサメチレンドデカミド(ナイロン612)、ポリオクタメチレンアジパミド(ナイロン86)、ポリデカメチレンアジパミド(ナイロン108)、カプロラクタム/ラウリルラクタム共重合体(ナイロン6/12)、カプロラクタム/ω-アミノノナン酸共重合体(ナイロン6/9)、カプロラクタム/ヘキサメチレンジアンモニウムアジペート共重合体(ナイロン6/66)、ラウリルラクタム/ヘキサメチレンジアンモニウムアジペート共重合体(ナイロン12/66)、エチレンジアミンアジパミド/ヘキサメチレンジアンモニウムアジペート共重合体(ナイロン26/66)、カプロラクタム/ヘキサメチレンジアンモニウムアジペート/ヘキサメチレンジアンモニウムセバケート共重合体(ナイロン66/610)、エチレンアンモニウムアジペート/ヘキサメチレンジアンモニウムアジペート/ヘキサメチレンジアンモニウムセバケート共重合体(ナイロン6/66/610)等の脂肪族ポリアミドや、ポリヘキサメチレンイソフタルアミド、ポリヘキサメチレンテレフタルアミド、ポリメタキシリレンアジパミド、ヘキサメチレンイソフタルアミド/テレフタルアミド共重合体、ポリ-p-フェニレンテレフタルアミドや、ポリ-p-フェニレン-3,4’-ジフェニルエーテルテレフタルアミド等の芳香族ポリアミド、非晶性ポリアミド、これらのポリアミド系重合体をメチレンベンジルアミン、メタキシレンジアミン等の芳香族アミンで変性したものやメタキシリレンジアンモニウムアジペート、あるいはこれらの末端変性ポリアミド系重合体等が挙げられる。なかでも、好ましくは末端変性ポリアミド系重合体である。
酸変性ポリオレフィン(c)としては、ポリオレフィンを酸でグラフト変性させて得られるグラフト変性ポリオレフィンや、オレフィンと酸を共重合させて得られるオレフィン系共重合体が挙げられる。これらは1種類を単独で用いてもよく、2種以上を組合せて用いてもよい。
なかでも、酸変性ポリオレフィン(c)としては、不飽和カルボン酸及び/又はその誘導体により変性された変性ポリオレフィンが好ましい。
ポリオレフィン系重合体(a)との相溶性に優れる観点から、酸変性ポリオレフィン(c)は、ポリオレフィン系重合体(a)と同じ種類のポリオレフィン系重合体を酸変性させたものであることが好ましい。例えば、ポリオレフィン系重合体(a)がポリプロピレンである場合には、酸変性ポリオレフィン(c)は酸変性ポリプロピレンであることが好ましい。ポリオレフィン系重合体(a)がポリエチレンである場合には、酸変性ポリオレフィン(c)は酸変性ポリエチレンであることが好ましい。
本発明の重合体組成物は、ポリオレフィン系重合体(a)100質量部に対して極性重合体(b)を0.1~20質量部、酸変性ポリオレフィン(d)を0.1~25質量部含有することが好ましい。
本発明の重合体組成物には、本発明の効果を著しく損なわない範囲で各種目的に応じて、ポリオレフィン系重合体(a)、極性重合体(b)、酸変性ポリオレフィン(c)、酸変性ポリオレフィン(d)以外の重合体や任意の添加剤等(以下、これらを「その他の成分」と称す。)を配合することができる。その他の成分は、1種類のみを用いても、2種類以上を任意の組合せと比率で併用してもよい。
本発明の重合体組成物を得るための各成分の混合方法について特に制限はなく、以下の方法などが挙げられる。
ポリオレフィン系重合体(a)、極性重合体(b)、及び酸変性ポリオレフィン(d)、必要に応じて用いられる酸変性ポリオレフィン(c)及びその他の成分を一度にドライブレンドして溶融混練する方法;
ポリオレフィン系重合体(a)、極性重合体(b)、及び酸変性ポリオレフィン(d)、必要に応じて用いられる酸変性ポリオレフィン(c)及びその他の成分の一部を予め溶融混練してから、他の成分を配合して溶融混練する方法;
ポリオレフィン系重合体(a)、極性重合体(b)、及び酸変性ポリオレフィン(d)、必要に応じて用いられる酸変性ポリオレフィン(c)及びその他の成分の一部又は全部を含有する多層構造体と、他の成分を配合して溶融混練する方法:
このような回収物を溶融混練する際に配合される添加剤を相溶化剤といい、ここでは、酸変性ポリオレフィン(d)を含有する相溶化剤が用いられる。
相溶化剤中の酸変性ポリオレフィン(d)の含有率は、5~100質量%が好適である。酸変性ポリオレフィン(d)の含有率は、10質量%以上がより好適であり、20質量%以上がさらに好適であり、50質量%以上が特に好適である。
本発明の重合体組成物を成形することで成形品(以下、「本発明の成形品」と称す場合がある。)とすることができる。
例えば、押出成形、ブロー成形、射出成形、熱成形等を挙げることができる。
以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味を持つものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。
<成分(A):エチレン・ブテン共重合体>
・A-1:三井化学社製 タフマー(登録商標)A35070S(MFR(190℃、荷重2.16kg):35g/10分、密度:0.870g/cm3)
・A-2:三井化学社製 タフマー(登録商標)A4085S(MFR(190℃、荷重2.16kg):3.6g/10分、密度:0.885g/cm3)
・A-3:三井化学社製 タフマー(登録商標)A20085S(MFR(190℃、荷重2.16kg):18g/10分、密度:0.885g/cm3)
・A-4:三井化学社製 タフマー(登録商標)A70050S(MFR(190℃、荷重2.16kg):70g/10分、密度:0.893g/cm3)
・有機過酸化物 日本油脂(株)製 パーヘキサ25B
・無水マレイン酸 市販品
<成分(D):エチレン・オクテン共重合体>
・D-1:Dow社製 AFFINITY(登録商標)GA1900(MFR(190℃、荷重2.16kg):1000g/10分、密度:0.870g/cm3)
・ポリエチレン:日本ポリエチレン社製 ノバテック(登録商標)UF230(MFR(190℃、荷重2.16kg):1g/10分、密度:0.921g/cm3)
・EVOH:三菱ケミカル社製 ソアノール(登録商標)DC3203RB(MFR(210℃、荷重2.16kg):3.8g/10分、密度:1.19g/cm3、エチレン単位含有率:32モル%、ケン化度:99.9モル%)
・接着性重合体:三菱ケミカル社製 モディック(登録商標)M512(MFR(190℃、荷重2.16kg):1.0g/10分、密度:0.900g/cm3)
<合成例1>
成分(A-1):100質量部、成分(B):0.03質量部、及び成分(C):0.15質量部をドライブレンドして混合し、2軸押出機(日本製鋼所社製、TEX25αIII、D=25mmφ、L/D=52.5)を用い、設定温度230℃、スクリュー回転数400rpm、押出量20kg/hで溶融混練し、ストランドカットによりペレット状の無水マレイン酸により変性された変性エチレン・ブテン共重合体(A’-1-1)を得た。得られた変性エチレン・ブテン共重合体(A’-1-1)について、前述の方法でMFR(190℃、2.16kg)、密度、グラフト率を測定した。測定結果を表-1に示す。
配合組成を表-1に示したように変更した以外は合成例1と同様にして、それぞれ変性共重合体(A’-1-2)、(A’-1-3)、(A’-1-4)、(A’-2)、(A’-3)、(A’-4)、(D’-1)を得た。得られた変性共重合体を用いて、合成例1と同様に、MFR(190℃、2.16kg)、密度、グラフト率を測定した。測定結果を表-1に示す。
<実施例1>
日本ポリエチレン社製 ノバテック(登録商標)UF230:77質量部、三菱ケミカル社製 ソアノール(登録商標)DC3203RB:10質量部、三菱ケミカル社製 モディック(登録商標)M512:10質量部に対し、合成例1の変性エチレン・ブテン共重合体(A’-1-1)を相溶化剤として3質量部、ドライブレンドして混合した。この混合物を、2軸押出機(日本製鋼所社製、TEX25αIII、D=25mmφ、L/D=52.5)を用い、設定温度210℃、スクリュー回転数400rpm、押出量20kg/hで溶融混練し、ストランドカットによりペレット状のリグラインド組成物を得た。この得られたリグラインド組成物を1pass品とした。得られた1pass品のリグラインド組成物について、上記記載の条件にて、再度2軸押出機にて溶融混練を実施し、得られたリグラインド組成物を2pass品とした。これらについて下記(1)~(4)の評価を行った。評価結果を表-2に示す。
配合組成を表-2に示したように変更した以外は実施例1と同様にして、1pass品および2pass品のリグラインド組成物を得た。得られたリグラインド組成物について、下記(1)~(4)の評価を行った。評価結果を表-2に示す。
(1)透明性
(株)GSIクレオス社製単層Tダイフィルム成形機(押出機:50mmφ、リップ開度:0.3mm)を用い、設定温度200℃、スクリュー回転数20rpmで膜厚0.1mmのフィルムを作製した。得られたフィルムを目視により比較し、透明性が高いフィルムを○、やや不透明なフィルムを△、不透明なフィルムを×とした。
上記にて作製した膜厚0.1mmのフィルムを用い、HAZEメーターを用いて内部ヘイズをn=3にて測定し、平均値を算出した。内部HAZEはポリエチレン中のEVOHの分散性を評価する指標であり、内部HAZE値が小さいほどEVOHが微分散しており外観が良好である。本評価では内部HAZE値が17%以下であるとEVOHの分散性が良好と評価する。
上記にて作製した膜厚0.1mmのフィルムを用い、JIS K7161に準拠する方法にて引張破断強度をn=3にて測定し、平均値を算出した。引張破断強度が25MPa以上であると機械特性が良好であると言える。
上記条件で押出を実施した際の、ダイスヘッドにおける1時間の押出後の低分子量熱分解物の析出量を計量した。異物付着量が0.25g以下であると熱安定性が良好であると言える。
表-2に示すように本発明の変性エチレン共重合体を用いた実施例1~4は、透明性を損なうことなく、異物付着量を無いもしくは少なくすることができた。また、内部HAZE、機械特性、リサイクル性にも優れる結果となった。
これに対して、MFRが2g/10分の変性エチレン・ブテン共重合体(A’-2)を用いた比較例1、MFRが13g/10分の変性エチレン・ブテン共重合体(A’-3)を用いた比較例2、MFRが59g/10分の変性エチレン・ブテン共重合体(A’-4)を用いた比較例3において、異物付着量が多い結果となった。
MFRが640g/10分の変性エチレン・オクテン共重合体(D’-1)を用いた比較例4は、2pass後のリグラインド組成物を用いたフィルム評価において内部HAZEが高く、リサイクル性に劣る結果となった。
比較例5は、相溶化剤を用いない例を示しており、内部HAZE、引張破断強度、異物付着量のいずれも2passの押出工程にて大きく性能悪化がみられる結果である。即ち、ポリエチレン、EVOH、接着性樹脂重合体から成るリグラインド組成物では再利用が困難である。
本出願は、2021年5月10日付で出願された日本特許出願2021-079460及び日本特許出願2021-079461に基づいており、その全体が引用により援用される。
Claims (13)
- エチレン単量体と炭素数4~8のα-オレフィン単量体の1種又は2種以上との共重合体を、不飽和カルボン酸及び/又はその無水物により変性した変性エチレン共重合体を含む相溶化剤であって、
該変性エチレン共重合体のメルトフローレート(MFR:190℃、2.16kg)が15~39g/10分である、相溶化剤。 - エチレン単量体と炭素数4~8のα-オレフィン単量体の1種又は2種以上との共重合体を、不飽和カルボン酸及び/又はその無水物により変性した変性エチレン共重合体を含むリサイクル助剤であって、
該変性エチレン共重合体のメルトフローレート(MFR:190℃、2.16kg)が15~39g/10分である、リサイクル助剤。 - エチレン単量体と炭素数4~8のα-オレフィン単量体の1種又は2種以上との共重合体を、不飽和カルボン酸及び/又はその無水物により変性した、メルトフローレート(MFR:190℃、2.16kg)が15~39g/10分の変性エチレン共重合体の存在下で、極性の重合体と非極性の重合体とを相溶化する相溶化方法。
- 前記変性エチレン共重合体の密度が0.855~0.895g/cm3である、請求項1に記載の相溶化剤。
- 前記変性エチレン共重合体の密度が0.855~0.895g/cm3である、請求項2に記載のリサイクル助剤。
- 前記変性エチレン共重合体の密度が0.855~0.895g/cm3である、請求項3に記載の相溶化方法。
- 前記変性エチレン共重合体のグラフト率が0.1~1.0質量%である、請求項1又は4に記載の相溶化剤。
- 前記変性エチレン共重合体のグラフト率が0.1~1.0質量%である、請求項2又は5に記載のリサイクル助剤。
- 前記変性エチレン共重合体のグラフト率が0.1~1.0質量%である、請求項3又は6に記載の相溶化方法。
- 前記変性エチレン共重合体がエチレン・ブテン共重合体である、請求項1又は4に記載の相溶化剤。
- 前記変性エチレン共重合体がエチレン・ブテン共重合体である、請求項2又は5に記載のリサイクル助剤。
- 前記変性エチレン共重合体がエチレン・ブテン共重合体である、請求項3又は6に記載の相溶化方法。
- 前記非極性の重合体がポリエチレン系重合体である、請求項3又は6に記載の相溶化方法。
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