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WO2024203319A1 - Resin composition, modifier, and composition containing said modifier - Google Patents

Resin composition, modifier, and composition containing said modifier Download PDF

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Publication number
WO2024203319A1
WO2024203319A1 PCT/JP2024/009700 JP2024009700W WO2024203319A1 WO 2024203319 A1 WO2024203319 A1 WO 2024203319A1 JP 2024009700 W JP2024009700 W JP 2024009700W WO 2024203319 A1 WO2024203319 A1 WO 2024203319A1
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WO
WIPO (PCT)
Prior art keywords
mass
resin composition
vinyl acetate
styrene
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/009700
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French (fr)
Japanese (ja)
Inventor
大資 釘本
元三 菊地
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
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Tosoh Corp
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Publication date
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Publication of WO2024203319A1 publication Critical patent/WO2024203319A1/en
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00Compositions 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04Homopolymers or copolymers of vinyl acetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions 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
    • C08L53/02Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a resin composition that contains a composition containing at least two types of ethylene-vinyl acetate copolymers with different vinyl acetate contents, and a styrene-based block copolymer.
  • the current process involves sorting collected plastic waste by material and then recycling it into products.
  • composite plastics In the case of multi-layer films or containers made of different types of plastics (hereinafter referred to as composite plastics), it is difficult to separate the individual materials, so they cannot be recycled and are currently either landfilled or incinerated.
  • compatibilizers is being considered as a means of recycling composite plastics.
  • Patent Document 1 shows that the physical properties of composite plastics, such as composite plastics of polyethylene (PE) and polyethylene terephthalate (PET), or composite plastics of polypropylene (PP) and acrylonitrile-butadiene-styrene copolymer (ABS), can be improved by adding a compatibilizer.
  • PE polyethylene
  • PET polyethylene terephthalate
  • PP polypropylene
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the present invention aims to provide a resin composition that is effective in reducing fisheyes that occur when a thermoplastic resin containing two or more plastic components is made into a film, and a modifier made from the resin composition. Furthermore, the present invention aims to provide a modifier that can produce a recycled film with good appearance from waste containing multiple plastics.
  • a resin composition containing a specific ethylene-vinyl acetate copolymer and a styrene-based block copolymer is highly effective at reducing fisheyes that occur when a thermoplastic resin containing two or more plastic components is made into a film, and thus completed the present invention.
  • the resin composition (A), which is one embodiment of the present invention, contains 50 to 99 parts by mass of a composition (a1) containing at least two types of ethylene-vinyl acetate copolymers differing in vinyl acetate content, and 1 to 50 parts by mass of a styrene-based block copolymer (a2) (where the sum of (a1) and (a2) is 100 parts by mass).
  • the resin composition of one embodiment of the present invention is effective as a modifier for thermoplastic resins containing two or more plastic components, and films of the modified thermoplastic resin have few fisheyes and excellent film appearance, making them useful for molded products that require these physical properties.
  • the resin composition (A) is a composition (a1) containing at least two kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents, and a styrene-based
  • the block copolymer (a2) is contained in an amount of 1 part by mass or more and 50 parts by mass or less.
  • Each ethylene-vinyl acetate copolymer in composition (a1) (hereinafter referred to as "EVA composition (a1)"), which comprises at least two types of ethylene-vinyl acetate copolymers differing in vinyl acetate content and which constitutes resin composition (A), can be obtained by a known manufacturing method. Specifically, manufacturing methods such as high-pressure radical polymerization, solution polymerization, or emulsion polymerization can be mentioned.
  • the ethylene-vinyl acetate copolymer can be conveniently selected from commercially available products, and is commercially available under the trade name Ultrathene from Tosoh Corporation and under the trade name Levaprene from Lanxess KK.
  • the vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 6% by mass or more and 90% by mass or less, and more preferably 15% by mass or more and 85% by mass or less.
  • a vinyl acetate content of 6% by mass or more is preferred because it has excellent compatibility with polyesters, while a vinyl acetate content of 90% by mass or less is preferred because it has excellent compatibility with polyolefins.
  • the ethylene-vinyl acetate copolymer contained in the EVA composition (a1) is preferably two or more types, more preferably three or more types.
  • the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the difference in vinyl acetate content between at least one pair of ethylene-vinyl acetate copolymers is preferably 40% by mass or less, more preferably 20% by mass or less, and most preferably 15% by mass or less.
  • the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer can be calculated as follows, for example, in a composition containing three types of ethylene-vinyl acetate copolymers having vinyl acetate contents of 25 mass%, 50 mass%, and 80 mass% (hereinafter, the vinyl acetate contents will be referred to as VAc25, VAc50, and VAc80, respectively).
  • the styrene-based block copolymer (a2) constituting the resin composition (A) may be composed of at least one polymer block mainly composed of styrene monomer units and at least one polymer block mainly composed of conjugated diene compound monomer units.
  • the styrene-based block copolymer (a2) may also be a hydrogenated product in which the double bonds are partially saturated/fully saturated by hydrogenation.
  • a polymer block mainly composed of styrene monomer units means that it contains 50% by mass or more of monomer units derived from styrene, when the monomer units in the polymer block are taken as 100% by mass.
  • the content of monomer units derived from styrene contained in a polymer block mainly composed of styrene monomer units may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.
  • a polymer block mainly composed of conjugated diene compound monomer units means that the polymer block contains 50% by mass or more of monomer units derived from a conjugated diene compound when the monomer units in the polymer block are taken as 100% by mass.
  • the content of monomer units derived from a conjugated diene compound contained in the polymer block mainly composed of conjugated diene compound monomer units may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.
  • Conjugated diene compounds constituting polymer blocks mainly composed of conjugated diene compound monomer units include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, phenylbutadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.
  • Polymer blocks mainly composed of conjugated diene compound monomer units may be composed of one type of these conjugated diene compounds alone, or two or more types. In addition, they may be subsequently hydrogenated to partially or completely saturate the double bonds.
  • styrene-based block copolymers (a2) include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS) which are hydrogenated products of SBS, and styrene-ethylene-propylene-styrene block copolymers (SEPS) which are hydrogenated products of SIS.
  • SBS styrene-ethylene-butene-styrene block copolymers
  • SEBS styrene-ethylene-butene-styrene block copolymers
  • SEBS styrene-ethylene-butene-styrene block copolymers
  • the proportion of the polymer block made of styrene in the styrene-based block copolymer is preferably 10% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. If it is 10% by mass or more, it is preferable because it has excellent compatibility with polyester, and if it is 50% by mass or less, it is preferable because it has excellent compatibility with polyolefin.
  • the mixing ratio of the EVA composition (a1) and the styrene-based block copolymer (a2) is 50 parts by mass or more and 99 parts by mass or less of the EVA composition (a1), and 1 part by mass or more and 50 parts by mass or less of the styrene-based block copolymer (a2) (where the total of (a1) and (a2) is 100 parts by mass), and preferably 60 parts by mass or more and 90 parts by mass or less of the EVA composition (a1), and 10 parts by mass or more and 40 parts by mass or less of the styrene-based block copolymer (a2) (where the total of (a1) and (a2) is 100 parts by mass).
  • the film appearance of the blended resin is further improved.
  • the fisheyes of the blended resin are further reduced.
  • the resin compatibilizer (hereinafter, may be referred to as a "modifier") according to one embodiment of the present invention contains a resin composition (A).
  • resin composition (A) as a modifier By blending resin composition (A) as a modifier with the base resin, the appearance of the film when the resin is molded into a film can be improved and fisheyes can be reduced.
  • the base material to be blended is a thermoplastic resin containing at least polyolefin and polyester (hereinafter referred to as "thermoplastic resin (B)").
  • the modifier can be used in any form, such as pellets or powder.
  • the thermoplastic resin (B) to which the modifier is added may contain at least polyolefin and polyester.
  • the thermoplastic resin (B) may contain thermoplastic resins other than polyolefin and polyester.
  • resin components other than polyolefin and polyester include polyamide, ethylene-vinyl alcohol copolymer, polystyrene, etc.
  • Polyolefins include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-acrylic acid ester copolymers, and ethylene-methacrylic acid ester copolymers.
  • Polyethylenes include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • Polyesters include polyethylene terephthalate, glycol-modified polyethylene terephthalate (PETG resin), polybutylene terephthalate, polylactic acid, etc.
  • polyamides examples include nylon 6, nylon 6,6, nylon 11, and nylon 12.
  • the polyolefins contained in the thermoplastic resin (B) are preferably high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene, as they have excellent film formability, and low-density polyethylene and linear low-density polyethylene are more preferable.
  • the polyester polyethylene terephthalate is preferable, as it has excellent film appearance.
  • the resin other than polyolefins and polyesters at least one member of the group consisting of polyamides and ethylene-vinyl alcohol copolymers is preferable.
  • the ratio of the resins constituting the thermoplastic resin (B) is preferably 70 parts by mass or more and 99 parts by mass or less of polyolefin and 1 part by mass or less and 30 parts by mass or less of polyester, because the strength of the film is excellent, and more preferably 80 parts by mass or more and 99 parts by mass or less of polyolefin and 1 part by mass or less and 20 parts by mass or less of polyester.
  • the ratio of the resins constituting the thermoplastic resin (B) is preferably 70 parts by mass or more and 98 parts by mass or less of polyolefin, 1 part by mass or more and 29 parts by mass or less of polyester, and more preferably 80 parts by mass or more and 98 parts by mass or less of polyolefin, 1 part by mass or more and 19 parts by mass or less of polyester, and 1 part by mass or more and 19 parts by mass or less of resins other than polyolefin and polyester.
  • the thermoplastic resin (B) may be an unused virgin resin, or a resin obtained by recovering plastic waste. In other words, it includes a form in which all of the one or more types of resin are unused resins, a form in which at least one of the one or more types of resins is a used resin, and a form in which all of the one or more types of resin are used resins.
  • the plastic waste is not particularly limited, but may be any of the following: burrs or film trimming loss generated in plastic molding factories, waste that cannot be used as products such as non-standard products, or waste from used plastic products collected from the city or consumers.
  • a recycled resin composition is produced as the resin composition by using plastic waste as a material for the resin composition.
  • a resin obtained by collecting plastic waste it may contain organic substances such as PVC resin, wax, adhesives, plasticizers, and antioxidants, and/or inorganic substances such as fillers as impurities.
  • a resin composition containing a resin composition (A) and a thermoplastic resin (B) is also included in one aspect of the present invention.
  • the mixing ratio of the resin composition (A) and the thermoplastic resin (B) in the resin composition is preferably 1 part by mass or more and 15 parts by mass or less of the resin composition (A) per 100 parts by mass of the thermoplastic resin (B), and more preferably 1 part by mass or more and 10 parts by mass or less of the resin composition (A).
  • the resin composition (A) is 1 part by mass or more, it is preferable because it is excellent in improving the film appearance and suppressing fish eyes, and when it is 15 parts by mass or less, it is preferable because it is excellent in film moldability.
  • Specific examples and preferred aspects of the resin composition (A) and the thermoplastic resin (B) are as described in the above item ⁇ Resin compatibilizer (modifier)>.
  • the melt mass flow rate (MFR) of the resin composition containing the resin composition (A) and the thermoplastic resin (B) is not particularly limited, but in order to provide excellent film moldability, the MFR measured under conditions of 190°C and a load of 2.16 kg is preferably 0.5 g/10 min or more and 30 g/10 min or less, more preferably 0.8 g/10 min or more and 20 g/10 min or less, and most preferably 1 g/10 min or more and 10 g/10 min or less.
  • the method for producing a resin composition containing the resin composition (A) and the thermoplastic resin (B) is not particularly limited as long as it is possible to disperse each component, and the composition can be produced using a commonly used resin kneading device.
  • kneading devices include single-screw extruders, twin-screw extruders, multi-screw extruders, Banbury mixers, pressure kneaders, rotating rolls, and internal mixers.
  • twin-screw extruders are preferred because of their excellent dispersibility and continuous productivity.
  • the screw rotation speed is not particularly limited, but kneading at 50 rpm to 3000 rpm is preferable, and more preferably 150 rpm to 1000 rpm.
  • a screw rotation speed of 50 rpm or more is preferable because it improves the dispersibility of each mixed component and results in excellent physical properties of the resulting resin, while a screw rotation speed of 3000 rpm or less is preferable because it prevents deterioration of the resin due to excessive shear heat generation and results in excellent physical properties of the resulting resin.
  • the kneading temperature is preferably above the melting point of the component with the lowest melting point in the thermoplastic resin (B) and below about 300°C.
  • the resin composition containing the resin composition (A) and the thermoplastic resin (B) may contain antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, antioxidants, antiblocking agents, flow improvers, release agents, flame retardants, colorants, inorganic neutralizing agents, hydrochloric acid absorbers, filler conductive agents, chain extenders, hydrolysis inhibitors, and the like, as long as the effects of the present invention are not impaired.
  • the resin composition containing the resin composition (A) and the thermoplastic resin (B) can be used in any form such as pellets or powder.
  • a molded article made of the resin composition containing the resin composition (A) and the thermoplastic resin (B) is also included in one aspect of the present invention.
  • the method for molding the resin composition is not particularly limited, but examples include profile extrusion, film, sheet, blow, injection, foaming, extrusion coating, and rotational molding. Among these, film is preferred due to the excellent moldability of the resin composition, which is one aspect of the present invention.
  • a film made of the resin composition is also included in one embodiment of the present invention.
  • the film molding method is not particularly limited, and examples thereof include inflation molding, coextrusion inflation molding, T-die molding, coextrusion T-die molding, calendar molding, and compression molding. Among these, inflation molding, coextrusion inflation molding, T-die molding, and coextrusion T-die molding are preferred because of their excellent productivity.
  • the film according to one embodiment of the present invention may be laminated with other films, and the lamination method is also not particularly limited, and examples thereof include dry lamination, extrusion lamination, and sandwich lamination.
  • the resin composition containing the resin composition (A) and the thermoplastic resin (B) of this embodiment described above can suppress the occurrence of fisheyes when made into a film.
  • fisheyes are particulate lumps that resemble fish eyes and are caused by foreign matter (unmelted material, etc.) that appears in the film.
  • the film of one embodiment of the present invention can be obtained by forming the resin composition into a film (molding into a film shape).
  • the film made of the resin composition may be a single layer or may be used in the form of a multilayer film.
  • the lamination structure of the multilayer film is not particularly limited, but may include, for example, not only the layer (I) of the resin composition of one embodiment of the present invention but also layers made of other components, such as a virgin resin layer (II), an adhesive layer (III) or a barrier layer (IV).
  • the "/" between layers means that the layers are adjacent to each other.
  • the thickness of the film made of the resin composition is not particularly limited, but is preferably 10 ⁇ m to 300 ⁇ m from the viewpoint of further suppressing the occurrence of fisheyes.
  • the film forming temperature is preferably in the range of 190°C to 250°C, more preferably in the range of 200°C to 250°C, and even more preferably in the range of 220°C to 250°C.
  • a forming temperature of 190°C or higher is preferable because it reduces the occurrence of fish eyes, while a forming temperature of 250°C or lower is preferable because it provides excellent film formability.
  • the film is useful as a packaging container for food, daily necessities, industrial parts, medicines, office supplies, chemical products, etc., a surface protection film, an agricultural film such as silage wrap, a shrink film, a transport bag, etc.
  • a resin composition (A) comprising 50 parts by mass or more and 99 parts by mass or less of a composition (a1) containing at least two kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents, and 1 part by mass or more and 50 parts by mass or less of a styrene-based block copolymer (a2) (wherein the total of (a1) and (a2) is 100 parts by mass).
  • the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer is 1 mass% or more, and further, the difference in vinyl acetate content between at least one pair of ethylene-vinyl acetate copolymers is 40 mass% or less.
  • the resin composition (A) according to any one of [1] to [3].
  • the resin composition (A) according to any one of [1] to [4], wherein the styrene-based block copolymer (a2) is a block copolymer having at least one polymer block mainly composed of styrene monomer units and at least one polymer block mainly composed of conjugated diene compound monomer units, or a hydrogenated product thereof.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • MFR Melt Mass Flow Rate
  • Example 1 As the resin composition (A), a resin composition having the following composition was used.
  • the resin composition was dry blended and melt-kneaded using a twin-screw extruder (manufactured by Technovel, product name ULT nano 25TW) with a screw diameter of 25 mm at a resin temperature of 160°C and a screw rotation speed of 150 rpm to obtain pellets of resin composition (A).
  • a twin-screw extruder manufactured by Technovel, product name ULT nano 25TW
  • thermoplastic resin (B) containing at least polyolefin and polyester:
  • thermoplastic resin (B) Linear low-density polyethylene (manufactured by Tosoh, MFR 2.0 g/10 min, product name Nipolon Z HF210K) 90 parts by mass Polyethylene terephthalate (manufactured by Unitika, product name MA-2103) 10 parts by mass
  • thermoplastic resin (B) The above resins were dry blended to obtain thermoplastic resin (B).
  • thermoplastic resin (B) Five parts by mass of resin composition (A) and 100 parts by mass of thermoplastic resin (B) were pre-blended in a tumbler mixer. Next, using a twin-screw extruder (manufactured by Technovel, product name ULT nano 25TW) with a screw diameter of 25 mm, the mixture was melt-mixed at a resin temperature of 260°C and a screw rotation speed of 300 rpm. After melt mixing, the mixture was cooled to room temperature to obtain resin composition pellets (molten mixture). The MFR of the resin composition was 3.0 g/10 min.
  • a single-layer film made of the resin composition pellets was obtained using a microcast molding machine (manufactured by Labtech Engineering).
  • the molding temperature was 200°C
  • the take-up speed was 2 m/min
  • the film width was 50 mm
  • the total film thickness was 50 ⁇ m.
  • Example 2 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 3 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 1 A monolayer film was obtained in the same manner as in Example 1, except that 100 parts by mass of a composite resin prepared by dry blending 90 parts by mass of linear low-density polyethylene (manufactured by Tosoh, MFR 2.0 g/10 min, product name Nipolon Z HF210K) and 10 parts by mass of polyethylene terephthalate (manufactured by Unitika, product name MA-2103) was used as the thermoplastic resin (B) containing at least polyolefin and polyester.
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 2 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 3 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 5 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Example 6 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Resin composition (A) 4 parts by mass of ethylene-vinyl acetate copolymer (a1-25) (product name Ultrathene 640, manufactured by Tosoh Corporation) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min.
  • Styrene-ethylene Butylene-styrene block copolymer (a2-13) manufactured by KRATON, styrene content 13% by mass, product name G1657VS
  • Example 7 A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
  • the MFR of the resin composition was 3.0 g/10 min.
  • Resin composition (A) 4 parts by mass of ethylene-vinyl acetate copolymer (a1-25) (product name Ultrathene 640, manufactured by Tosoh Corporation) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min.
  • Styrene-ethylene Butylene-styrene block copolymer (a2-30) manufactured by KRATON, styrene content 30% by mass, product name G1726MS 1 part by mass
  • the films of Examples 1 to 3 had two or less fisheyes, confirming that the occurrence of fisheyes was suppressed. In addition, it was confirmed that the surface smoothness was good and the film appearance was excellent.
  • Films made from the resin composition of the present invention are useful as packaging containers for food, daily necessities, industrial parts, pharmaceuticals, office supplies, chemical products, etc., surface protection films, agricultural films such as silage wrap, shrink films, transport bags, etc.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present disclosure relates to a resin composition (A) comprising: 50 parts by mass to 99 parts by mass inclusive of a composition (a1) comprising at least two ethylene-(vinyl acetate) copolymers having different vinyl acetate contents from each other; and 1 part by mass to 50 parts by mass inclusive of a styrene-based block copolymer (a2) (wherein the total amount of the components (a1) and (a2) is 100 parts by mass).

Description

樹脂組成物、改質剤およびその改質剤を含む組成物Resin composition, modifier and composition containing the modifier

 本発明は、酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物と、スチレン系ブロック共重合体とを含む樹脂組成物に関するものである。 The present invention relates to a resin composition that contains a composition containing at least two types of ethylene-vinyl acetate copolymers with different vinyl acetate contents, and a styrene-based block copolymer.

 近年、プラスチックによる環境汚染問題への関心が高まっており、プラスチック製品のマテリアルリサイクルが促進されている。 In recent years, interest in the problem of environmental pollution caused by plastics has increased, and material recycling of plastic products has been promoted.

 プラスチックのマテリアルリサイクルでは、一般的に、回収したプラスチック廃棄物中に異種のプラスチックが混在した状態でリサイクルすると、互いの相溶性が悪いことからリサイクルされたプラスチックの物性が低下する問題が生じる。 In the case of plastic material recycling, if different types of plastics are mixed in the collected plastic waste, there is a problem that the physical properties of the recycled plastic deteriorate due to their poor compatibility with each other.

 そのため、現在は回収したプラスチック廃棄物を素材毎に選別したのち、製品へ再生するという工程がとられている。 As a result, the current process involves sorting collected plastic waste by material and then recycling it into products.

 しかしながら、異種のプラスチックが積層された多層フィルムまたは多層容器など(以下、複合プラスチック)では、素材毎に分別することが困難であることからリサイクルすることができず、埋立てまたは焼却処理されているのが現状である。 However, in the case of multi-layer films or containers made of different types of plastics (hereinafter referred to as composite plastics), it is difficult to separate the individual materials, so they cannot be recycled and are currently either landfilled or incinerated.

 このような背景の中、複合プラスチックをリサイクルする手段として、相溶化剤の添加が検討されている。 Against this background, the addition of compatibilizers is being considered as a means of recycling composite plastics.

 例えば、特許文献1にはポリエチレン(PE)とポリエチレンテレフタレート(PET)との複合プラスチック、または、ポリプロピレン(PP)とアクリロニトリル-ブタジエン-スチレン共重合体(ABS)との複合プラスチックなどに相溶化剤を添加することにより複合プラスチックの物性を向上できることが示されている。 For example, Patent Document 1 shows that the physical properties of composite plastics, such as composite plastics of polyethylene (PE) and polyethylene terephthalate (PET), or composite plastics of polypropylene (PP) and acrylonitrile-butadiene-styrene copolymer (ABS), can be improved by adding a compatibilizer.

 しかしながら、本発明者らが複合プラスチックのリサイクルを検討する中で、ポリオレフィンにポリエステルを含む樹脂をフィルム化した際にフィッシュアイと呼ばれる外観不良が多発することが判明した。 However, while the inventors were investigating the recycling of composite plastics, they discovered that when a resin containing polyester in polyolefin was made into a film, a defect in appearance known as fish eyes frequently occurred.

日本国特開2001-220473号公報Japanese Patent Application Publication No. 2001-220473

 本発明によれば、2種以上のプラスチック成分を含む熱可塑性樹脂をフィルム化した際に発生するフィッシュアイの低減に有効な樹脂組成物およびその樹脂組成物からなる改質剤を提供することを目的とする。更には、本発明によれば、複数のプラスチックを含む廃棄物から外観が良好なリサイクルフィルムが得られる改質剤を提供することを目的とする。 The present invention aims to provide a resin composition that is effective in reducing fisheyes that occur when a thermoplastic resin containing two or more plastic components is made into a film, and a modifier made from the resin composition. Furthermore, the present invention aims to provide a modifier that can produce a recycled film with good appearance from waste containing multiple plastics.

 本発明者らは、前記課題を解決すべく鋭意検討した結果、特定のエチレン-酢酸ビニル共重合体とスチレン系ブロック共重合体を配合した樹脂組成物が、2種以上のプラスチック成分を含む熱可塑性樹脂をフィルム化した際に発生するフィッシュアイの低減効果に優れることを見出し、本発明を完成するに至った。 As a result of intensive research aimed at solving the above problems, the inventors discovered that a resin composition containing a specific ethylene-vinyl acetate copolymer and a styrene-based block copolymer is highly effective at reducing fisheyes that occur when a thermoplastic resin containing two or more plastic components is made into a film, and thus completed the present invention.

 本発明の一態様である樹脂組成物(A)は、酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物(a1)を50質量部以上99質量部以下、スチレン系ブロック共重合体(a2)1質量部以上50質量部以下(ここで(a1)および(a2)の合計は100質量部とする)を含む。 The resin composition (A), which is one embodiment of the present invention, contains 50 to 99 parts by mass of a composition (a1) containing at least two types of ethylene-vinyl acetate copolymers differing in vinyl acetate content, and 1 to 50 parts by mass of a styrene-based block copolymer (a2) (where the sum of (a1) and (a2) is 100 parts by mass).

 本発明の一態様である樹脂組成物は2種以上のプラスチック成分を含む熱可塑性樹脂の改質剤として有効であり、その改質された熱可塑性樹脂のフィルムは、フィッシュアイが少なく、フィルム外観に優れており、これらの物性を要求される成形品に有用である。 The resin composition of one embodiment of the present invention is effective as a modifier for thermoplastic resins containing two or more plastic components, and films of the modified thermoplastic resin have few fisheyes and excellent film appearance, making them useful for molded products that require these physical properties.

 以下、本発明をその好適な実施形態に即して詳細に説明する。 The present invention will now be described in detail with reference to preferred embodiments.

 <樹脂組成物(A)>
 本発明の一態様である樹脂組成物(A)は、酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物(a1)を50質量部以上99質量部以下、スチレン系ブロック共重合体(a2)1質量部以上50質量部以下含むものである。
<Resin composition (A)>
The resin composition (A) according to one embodiment of the present invention is a composition (a1) containing at least two kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents, and a styrene-based The block copolymer (a2) is contained in an amount of 1 part by mass or more and 50 parts by mass or less.

 樹脂組成物(A)を構成する、酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物(a1)(以下、「EVA組成物(a1)」という)における各エチレン-酢酸ビニル共重合体は、公知の製造方法により得ることができる。具体的には、高圧法ラジカル重合、溶液重合または乳化重合などの製造方法が挙げられる。エチレン-酢酸ビニル共重合体は市販品の中から便宜選択することができ、東ソー株式会社からウルトラセンの商品名で、ランクセス株式会社からレバプレンの商品名で各々市販されている。 Each ethylene-vinyl acetate copolymer in composition (a1) (hereinafter referred to as "EVA composition (a1)"), which comprises at least two types of ethylene-vinyl acetate copolymers differing in vinyl acetate content and which constitutes resin composition (A), can be obtained by a known manufacturing method. Specifically, manufacturing methods such as high-pressure radical polymerization, solution polymerization, or emulsion polymerization can be mentioned. The ethylene-vinyl acetate copolymer can be conveniently selected from commercially available products, and is commercially available under the trade name Ultrathene from Tosoh Corporation and under the trade name Levaprene from Lanxess KK.

 エチレン-酢酸ビニル共重合体のJIS K6924-1で測定した酢酸ビニル含有量は、6質量%以上90質量%以下であることが好ましく、より好ましくは15質量%以上85質量%以下である。酢酸ビニル含有量が6質量%以上であればポリエステルとの相溶性に優れ、酢酸ビニル含有量が90質量%以下であればポリオレフィンとの相溶性に優れることから好ましい。 The vinyl acetate content of the ethylene-vinyl acetate copolymer, measured according to JIS K6924-1, is preferably 6% by mass or more and 90% by mass or less, and more preferably 15% by mass or more and 85% by mass or less. A vinyl acetate content of 6% by mass or more is preferred because it has excellent compatibility with polyesters, while a vinyl acetate content of 90% by mass or less is preferred because it has excellent compatibility with polyolefins.

 EVA組成物(a1)に含まれるエチレン-酢酸ビニル共重合体は、相溶性の観点から、2種以上が好ましく、より好ましくは3種以上である。また、各エチレン-酢酸ビニル共重合体の酢酸ビニル含量の差は1質量%以上であることが好ましく、より好ましくは5質量%以上である。さらに少なくとも一組のエチレン-酢酸ビニル共重合体の酢酸ビニル含量の差は40質量%以下であることが好ましく、より好ましくは20質量%以下であり、最も好ましくは15質量%以下である。 From the viewpoint of compatibility, the ethylene-vinyl acetate copolymer contained in the EVA composition (a1) is preferably two or more types, more preferably three or more types. In addition, the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer is preferably 1% by mass or more, more preferably 5% by mass or more. Furthermore, the difference in vinyl acetate content between at least one pair of ethylene-vinyl acetate copolymers is preferably 40% by mass or less, more preferably 20% by mass or less, and most preferably 15% by mass or less.

 ここで、EVA組成物(a1)において、各エチレン-酢酸ビニル共重合体の酢酸ビニル含量の差とは、例えば、酢酸ビニル含量25質量%、50質量%、80質量%の3種のエチレン-酢酸ビニル共重合体(以下、酢酸ビニル含量をそれぞれ。VAc25、VAc50、VAc80と表記する)を含む組成物においては、次のように算出できる。
 VAc50 - VAc25 = 25質量%
 VAc80 - VAc50 = 30質量%
 VAc80 - VAc25 = 55質量%
Here, in the EVA composition (a1), the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer can be calculated as follows, for example, in a composition containing three types of ethylene-vinyl acetate copolymers having vinyl acetate contents of 25 mass%, 50 mass%, and 80 mass% (hereinafter, the vinyl acetate contents will be referred to as VAc25, VAc50, and VAc80, respectively).
VAc50 - VAc25 = 25% by mass
VAc80 - VAc50 = 30% by mass
VAc80 - VAc25 = 55% by mass

 樹脂組成物(A)を構成するスチレン系ブロック共重合体(a2)は、スチレン単量体単位を主体とする少なくとも1個の重合体ブロックと、共役ジエン化合物単量体単位を主体とする少なくとも1個の重合体ブロックとから構成されていてもよい。また、スチレン系ブロック共重合体(a2)は、水素添加されて二重結合が一部飽和/全て飽和された水素添加物であってもよい。 The styrene-based block copolymer (a2) constituting the resin composition (A) may be composed of at least one polymer block mainly composed of styrene monomer units and at least one polymer block mainly composed of conjugated diene compound monomer units. The styrene-based block copolymer (a2) may also be a hydrogenated product in which the double bonds are partially saturated/fully saturated by hydrogenation.

 本明細書において、スチレン単量体単位を主体とする重合体ブロックとは、重合体ブロック中の単量体単位を100質量%としたときに、スチレンに由来する単量体単位を50質量%以上含むことを示す。スチレン単量体単位を主体とする重合体ブロックに含まれるスチレンに由来する単量体単位の含有量は60質量%以上、70質量%以上、80質量%以上、90質量%以上、95質量%以上、99質量%以上または100質量%であってもよい。 In this specification, a polymer block mainly composed of styrene monomer units means that it contains 50% by mass or more of monomer units derived from styrene, when the monomer units in the polymer block are taken as 100% by mass. The content of monomer units derived from styrene contained in a polymer block mainly composed of styrene monomer units may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.

 本明細書において、共役ジエン化合物単量体単位を主体とする重合体ブロックとは、重合体ブロック中の単量体単位を100質量%としたときに、共役ジエン化合物に由来する単量体単位を50質量%以上含むことを示す。共役ジエン化合物単量体単位を主体とする重合体ブロックに含まれる共役ジエン化合物に由来する単量体単位の含有量は60質量%以上、70質量%以上、80質量%以上、90質量%以上、95質量%以上、99質量%以上または100質量%であってもよい。 In this specification, a polymer block mainly composed of conjugated diene compound monomer units means that the polymer block contains 50% by mass or more of monomer units derived from a conjugated diene compound when the monomer units in the polymer block are taken as 100% by mass. The content of monomer units derived from a conjugated diene compound contained in the polymer block mainly composed of conjugated diene compound monomer units may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.

 共役ジエン化合物単量体単位を主体とする重合体ブロックを構成する共役ジエン化合物としては、1,3-ブタジエン、イソプレン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエン、2-メチル-1,3-ペンタジエン、1,3-ヘキサジエン、フェニルブタジエン、4,5-ジエチル-1,3-オクタジエン、3-ブチル-1,3-オクタジエンなどが挙げられる。共役ジエン化合物単量体単位を主体とする重合体ブロックは、これらの共役ジエン化合物の1種単独で構成されていても、2種以上から構成されていてもよい。また、その後に水素添加されて二重結合が一部飽和/全て飽和された状態でもよい。 Conjugated diene compounds constituting polymer blocks mainly composed of conjugated diene compound monomer units include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, phenylbutadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Polymer blocks mainly composed of conjugated diene compound monomer units may be composed of one type of these conjugated diene compounds alone, or two or more types. In addition, they may be subsequently hydrogenated to partially or completely saturate the double bonds.

 スチレン系ブロック共重合体(a2)の具体例としては、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-イソプレン-スチレンブロック共重合体(SIS)、SBSの水素添加物であるスチレン-エチレン・ブテン-スチレンブロック共重合体(SEBS)、SISの水素添加物であるスチレン-エチレン・プロピレン-スチレンブロック共重合体(SEPS)などが挙げられる。これらの中でスチレン-エチレン・ブテン-スチレンブロック共重合体(SEBS)がエチレン-酢酸ビニル共重合体およびポリオレフィンまたはポリエステルとの相溶性の点で好ましい。 Specific examples of styrene-based block copolymers (a2) include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS) which are hydrogenated products of SBS, and styrene-ethylene-propylene-styrene block copolymers (SEPS) which are hydrogenated products of SIS. Among these, styrene-ethylene-butene-styrene block copolymers (SEBS) are preferred in terms of compatibility with ethylene-vinyl acetate copolymers and polyolefins or polyesters.

 スチレン系ブロック共重合体中のスチレンからなる重合体ブロックの割合は、10質量%以上50質量%以下が好ましく、より好ましくは10質量%以上30質量%以下である。10質量%以上であればポリエステルとの相溶性に優れるため好ましく、50質量%以下であればポリオレフィンとの相溶性に優れるため好ましい。 The proportion of the polymer block made of styrene in the styrene-based block copolymer is preferably 10% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. If it is 10% by mass or more, it is preferable because it has excellent compatibility with polyester, and if it is 50% by mass or less, it is preferable because it has excellent compatibility with polyolefin.

 樹脂組成物(A)において、EVA組成物(a1)とスチレン系ブロック共重合体(a2)の混合比率は、EVA組成物(a1)を50質量部以上99質量部以下、スチレン系ブロック共重合体(a2)を1質量部以上50質量部以下(ここで(a1)および(a2)の合計は100質量部とする)であり、EVA組成物(a1)を60質量部以上90質量部以下、スチレン系ブロック共重合体(a2)を10質量部以上40質量部以下(ここで(a1)および(a2)の合計は100質量部とする)であることが好ましい。EVA組成物(a1)を50質量部以上99質量部以下含むことで、配合した樹脂のフィルム外観をより向上させる。一方、スチレン系ブロック共重合体(a2)を1質量部以上50質量部以下含むことで、配合した樹脂のフィッシュアイをより低減させる。 In the resin composition (A), the mixing ratio of the EVA composition (a1) and the styrene-based block copolymer (a2) is 50 parts by mass or more and 99 parts by mass or less of the EVA composition (a1), and 1 part by mass or more and 50 parts by mass or less of the styrene-based block copolymer (a2) (where the total of (a1) and (a2) is 100 parts by mass), and preferably 60 parts by mass or more and 90 parts by mass or less of the EVA composition (a1), and 10 parts by mass or more and 40 parts by mass or less of the styrene-based block copolymer (a2) (where the total of (a1) and (a2) is 100 parts by mass). By including 50 parts by mass or more and 99 parts by mass or less of the EVA composition (a1), the film appearance of the blended resin is further improved. On the other hand, by including 1 part by mass or more and 50 parts by mass or less of the styrene-based block copolymer (a2), the fisheyes of the blended resin are further reduced.

 以下に本発明の一態様である改質剤について詳細に説明する。 The modifier, which is one aspect of the present invention, is described in detail below.

 <樹脂相溶化剤(改質剤)>
 本発明の一態様である樹脂相溶化剤(以下、「改質剤」と示す場合がある)は、樹脂組成物(A)を含むものである。
<Resin Compatibilizer (Modifier)>
The resin compatibilizer (hereinafter, may be referred to as a "modifier") according to one embodiment of the present invention contains a resin composition (A).

 樹脂組成物(A)を改質剤として母材となる樹脂に配合することで該樹脂をフィルム成形した際のフィルム外観が向上し、フィッシュアイを低減することができる。 By blending resin composition (A) as a modifier with the base resin, the appearance of the film when the resin is molded into a film can be improved and fisheyes can be reduced.

 また、配合する母材は少なくともポリオレフィンおよびポリエステルを含む熱可塑性樹脂(以下、「熱可塑性樹脂(B)」という)であることが好ましい。 In addition, it is preferable that the base material to be blended is a thermoplastic resin containing at least polyolefin and polyester (hereinafter referred to as "thermoplastic resin (B)").

 前記改質剤は、ペレットまたはパウダーなどの任意の形態で使用することができる。 The modifier can be used in any form, such as pellets or powder.

 前記改質剤を配合する熱可塑性樹脂(B)としては、少なくともポリオレフィンとポリエステルを含んでいればよい。つまり熱可塑性樹脂(B)は、ポリオレフィンとポリエステル以外の熱可塑性樹脂を含むものであってもよい。ポリオレフィンとポリエステル以外の樹脂の成分としては、ポリアミド、エチレン-ビニルアルコール共重合体、ポリスチレンなどが挙げられる。 The thermoplastic resin (B) to which the modifier is added may contain at least polyolefin and polyester. In other words, the thermoplastic resin (B) may contain thermoplastic resins other than polyolefin and polyester. Examples of resin components other than polyolefin and polyester include polyamide, ethylene-vinyl alcohol copolymer, polystyrene, etc.

 ポリオレフィンとしては、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレンーアクリル酸エステル共重合体、エチレンーメタクリル酸エステル共重合体などが挙げられる。ポリエチレンとしては、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレンが挙げられる。 Polyolefins include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-acrylic acid ester copolymers, and ethylene-methacrylic acid ester copolymers. Polyethylenes include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene.

 ポリエステルとしては、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタレート(PETG樹脂)、ポリブチレンテレフタレート、ポリ乳酸などが挙げられる。 Polyesters include polyethylene terephthalate, glycol-modified polyethylene terephthalate (PETG resin), polybutylene terephthalate, polylactic acid, etc.

 ポリアミドとしては、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12などが挙げられる。 Examples of polyamides include nylon 6, nylon 6,6, nylon 11, and nylon 12.

 これらの中で、熱可塑性樹脂(B)に含まれるポリオレフィンとしては、フィルム成形性に優れることから高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレンが好ましく、低密度ポリエチレン、直鎖状低密度ポリエチレンがより好ましい。ポリエステルとしてはフィルム外観に優れることからポリエチレンテレフタレートが好ましい。ポリオレフィンおよびポリエステル以外の樹脂としてはポリアミド、エチレン-ビニルアルコール共重合体から成る群の少なくとも1種が好ましい。 Among these, the polyolefins contained in the thermoplastic resin (B) are preferably high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene, as they have excellent film formability, and low-density polyethylene and linear low-density polyethylene are more preferable. As the polyester, polyethylene terephthalate is preferable, as it has excellent film appearance. As the resin other than polyolefins and polyesters, at least one member of the group consisting of polyamides and ethylene-vinyl alcohol copolymers is preferable.

 熱可塑性樹脂(B)を構成する樹脂の比率としては、フィルムの強度に優れることからポリオレフィンが70質量部以上99質量部以下、ポリエステルが1質量部以上30質量部以下であることが好ましく、ポリオレフィンが80質量部以上99質量部以下、ポリエステルが1質量部以上20質量部以下であることがより好ましい。ポリオレフィンおよびポリエステル以外の樹脂を含む場合は、熱可塑性樹脂(B)を構成する樹脂の比率としては、ポリオレフィンが70質量部以上98質量部以下、ポリエステルが1質量部以上29質量部以下、ポリオレフィンおよびポリエステル以外の樹脂が1質量部以上29質量部以下であることが好ましく、ポリオレフィンが80質量部以上98質量部以下、ポリエステルが1質量部以上19質量部以下、ポリオレフィンおよびポリエステル以外の樹脂が1質量部以上19質量部以下であることがより好ましい。 The ratio of the resins constituting the thermoplastic resin (B) is preferably 70 parts by mass or more and 99 parts by mass or less of polyolefin and 1 part by mass or less and 30 parts by mass or less of polyester, because the strength of the film is excellent, and more preferably 80 parts by mass or more and 99 parts by mass or less of polyolefin and 1 part by mass or less and 20 parts by mass or less of polyester. When resins other than polyolefin and polyester are contained, the ratio of the resins constituting the thermoplastic resin (B) is preferably 70 parts by mass or more and 98 parts by mass or less of polyolefin, 1 part by mass or more and 29 parts by mass or less of polyester, and more preferably 80 parts by mass or more and 98 parts by mass or less of polyolefin, 1 part by mass or more and 19 parts by mass or less of polyester, and 1 part by mass or more and 19 parts by mass or less of resins other than polyolefin and polyester.

 熱可塑性樹脂(B)は、未使用のバージン樹脂でもよく、プラスチック廃棄物を回収して得られた樹脂でもよい。すなわち、1種または複数種の樹脂のすべてが未使用の樹脂である形態、1種または複数種の樹脂のうちの少なくとも1種が使用済みの樹脂である形態が含まれ、1種または複数種の樹脂のすべてが使用済みの樹脂である形態も含まれる。 The thermoplastic resin (B) may be an unused virgin resin, or a resin obtained by recovering plastic waste. In other words, it includes a form in which all of the one or more types of resin are unused resins, a form in which at least one of the one or more types of resins is a used resin, and a form in which all of the one or more types of resin are used resins.

 プラスチック廃棄物は特に限定されるものではないが、プラスチック成形工場などで発生するバリもしくはフィルムのトリミングロス、規格外品などの製品にならない廃棄物、または、市中もしくは消費者から回収した使用済みプラスチック製品の廃棄物のいずれであってもよい。本発明の実施形態において、樹脂組成物の材料としてプラスチック廃棄物を用いることにより、樹脂組成物としてリサイクル樹脂組成物が製造される。また、プラスチック廃棄物を回収して得られた樹脂を使用する場合、不純物として塩ビ樹脂、ワックス、接着剤、可塑剤、酸化防止剤などの有機物および/またはフィラーなどの無機物を不純物として含んでもよい。 The plastic waste is not particularly limited, but may be any of the following: burrs or film trimming loss generated in plastic molding factories, waste that cannot be used as products such as non-standard products, or waste from used plastic products collected from the city or consumers. In an embodiment of the present invention, a recycled resin composition is produced as the resin composition by using plastic waste as a material for the resin composition. In addition, when using a resin obtained by collecting plastic waste, it may contain organic substances such as PVC resin, wax, adhesives, plasticizers, and antioxidants, and/or inorganic substances such as fillers as impurities.

 <樹脂組成物>
 樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物も本発明の一態様に含まれる。当該樹脂組成物中の樹脂組成物(A)と熱可塑性樹脂(B)との混合比率は、熱可塑性樹脂(B)100質量部に対して樹脂組成物(A)を1質量部以上15質量部以下含むことが好ましく、樹脂組成物(A)を1質量部以上10質量部以下含むことがより好ましい。樹脂組成物(A)が1質量部以上の場合はフィルム外観の向上およびフィッシュアイの抑制効果に優れるため好ましく、15質量部以下であればフィルム成形性に優れるため好ましい。樹脂組成物(A)および熱可塑性樹脂(B)の具体例および好ましい態様は、前記<樹脂相溶化剤(改質剤)>の項目で説明したとおりである。
<Resin Composition>
A resin composition containing a resin composition (A) and a thermoplastic resin (B) is also included in one aspect of the present invention. The mixing ratio of the resin composition (A) and the thermoplastic resin (B) in the resin composition is preferably 1 part by mass or more and 15 parts by mass or less of the resin composition (A) per 100 parts by mass of the thermoplastic resin (B), and more preferably 1 part by mass or more and 10 parts by mass or less of the resin composition (A). When the resin composition (A) is 1 part by mass or more, it is preferable because it is excellent in improving the film appearance and suppressing fish eyes, and when it is 15 parts by mass or less, it is preferable because it is excellent in film moldability. Specific examples and preferred aspects of the resin composition (A) and the thermoplastic resin (B) are as described in the above item <Resin compatibilizer (modifier)>.

 樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物のメルトマスフローレート(MFR)は特に限定されないが、フィルム成形性に優れることから、190℃、2.16kg荷重の条件で測定したMFRが0.5g/10分以上30g/10分以下であることが好ましく、0.8g/10分以上20g/10分以下であることがより好ましく、1g/10分以上10g/10分以下であることが最も好ましい。 The melt mass flow rate (MFR) of the resin composition containing the resin composition (A) and the thermoplastic resin (B) is not particularly limited, but in order to provide excellent film moldability, the MFR measured under conditions of 190°C and a load of 2.16 kg is preferably 0.5 g/10 min or more and 30 g/10 min or less, more preferably 0.8 g/10 min or more and 20 g/10 min or less, and most preferably 1 g/10 min or more and 10 g/10 min or less.

 樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物の製造方法は、各成分を分散できれば特に制限はなく、通常用いられる樹脂の混練装置により製造することができる。例えば、単軸押出機、二軸押出機、多軸押出機、バンバリーミキサー、加圧ニーダ-、回転ロール、インターナルミキサーなどの混練装置が挙げられる。この中で、分散性および連続生産性に優れることから、二軸押出機が好ましい。 The method for producing a resin composition containing the resin composition (A) and the thermoplastic resin (B) is not particularly limited as long as it is possible to disperse each component, and the composition can be produced using a commonly used resin kneading device. Examples of kneading devices include single-screw extruders, twin-screw extruders, multi-screw extruders, Banbury mixers, pressure kneaders, rotating rolls, and internal mixers. Among these, twin-screw extruders are preferred because of their excellent dispersibility and continuous productivity.

 二軸押出機で混練を行う場合のスクリュ回転数は特に制限されないが、50rpm以上3000rpm以下で混練することが好ましく、より好ましくは150rpm以上1000rpm以下である。スクリュ回転数50rpm以上であれば混合した各成分の分散性が向上し、得られた樹脂の物性に優れるため好ましく、スクリュ回転数3000rpm以下であれば過剰なせん断発熱による樹脂の劣化が生じないことから、得られた樹脂の物性に優れるため好ましい。 When kneading with a twin-screw extruder, the screw rotation speed is not particularly limited, but kneading at 50 rpm to 3000 rpm is preferable, and more preferably 150 rpm to 1000 rpm. A screw rotation speed of 50 rpm or more is preferable because it improves the dispersibility of each mixed component and results in excellent physical properties of the resulting resin, while a screw rotation speed of 3000 rpm or less is preferable because it prevents deterioration of the resin due to excessive shear heat generation and results in excellent physical properties of the resulting resin.

 混練温度は熱可塑性樹脂(B)の中で最も融点が低い成分の融点以上300℃以下程度が好ましい。 The kneading temperature is preferably above the melting point of the component with the lowest melting point in the thermoplastic resin (B) and below about 300°C.

 また、樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物は、本発明の効果を損なわない範囲で、帯電防止剤、光安定剤、紫外線吸収剤、造核剤、酸化防止剤、ブロッキング防止剤、流動性改良剤、離型剤、難燃剤、着色剤、無機系中和剤、塩酸吸収剤、充填剤導電剤、鎖長延長剤、加水分解防止剤などが用いられてもよい。 In addition, the resin composition containing the resin composition (A) and the thermoplastic resin (B) may contain antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, antioxidants, antiblocking agents, flow improvers, release agents, flame retardants, colorants, inorganic neutralizing agents, hydrochloric acid absorbers, filler conductive agents, chain extenders, hydrolysis inhibitors, and the like, as long as the effects of the present invention are not impaired.

 <成形体>
 また、樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物は、ペレットまたはパウダーなどの任意の形態で使用することができる。樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物からなる成形体も本発明の一態様に含まれる。
<Molded body>
In addition, the resin composition containing the resin composition (A) and the thermoplastic resin (B) can be used in any form such as pellets or powder. A molded article made of the resin composition containing the resin composition (A) and the thermoplastic resin (B) is also included in one aspect of the present invention.

 前記樹脂組成物の成形方法としては特に制限されないが、例えば異形押出、フィルム、シート、ブロー、射出、発泡、押出コーティング、回転成形などが挙げられ、この中で本発明の一態様である樹脂組成物の成形性に優れることからフィルムが好ましい。 The method for molding the resin composition is not particularly limited, but examples include profile extrusion, film, sheet, blow, injection, foaming, extrusion coating, and rotational molding. Among these, film is preferred due to the excellent moldability of the resin composition, which is one aspect of the present invention.

 前記樹脂組成物からなるフィルムも本発明の一態様に含まれる。フィルムの成形方法については、特に制限はなく、インフレーション成形法、共押出インフレーション成形法、Tダイ成形法、共押出Tダイ成形法、カレンダー成形法、圧縮成形法などを例示できる。これらの中で、生産性に優れることからインフレーション成形法、共押出インフレーション成形法、Tダイ成形法、共押出Tダイ成形法が好ましい。また、本発明の一態様に係るフィルムは他のフィルムと積層してもよく、積層方法についても同様に特に制限はないが、ドライラミネート法、押出ラミネート法、サンドウィッチラミネート法などを例示できる。 A film made of the resin composition is also included in one embodiment of the present invention. The film molding method is not particularly limited, and examples thereof include inflation molding, coextrusion inflation molding, T-die molding, coextrusion T-die molding, calendar molding, and compression molding. Among these, inflation molding, coextrusion inflation molding, T-die molding, and coextrusion T-die molding are preferred because of their excellent productivity. The film according to one embodiment of the present invention may be laminated with other films, and the lamination method is also not particularly limited, and examples thereof include dry lamination, extrusion lamination, and sandwich lamination.

 以上説明した本実施形態の樹脂組成物(A)および熱可塑性樹脂(B)を含む樹脂組成物は、フィルム化した際にフィッシュアイの発生を抑制することができる。なお、フィッシュアイは、フィルムに生じた異物(未溶融物など)が原因となって生じる魚眼のような粒子状の塊である。 The resin composition containing the resin composition (A) and the thermoplastic resin (B) of this embodiment described above can suppress the occurrence of fisheyes when made into a film. Note that fisheyes are particulate lumps that resemble fish eyes and are caused by foreign matter (unmelted material, etc.) that appears in the film.

 本発明の一態様であるフィルムは、前記樹脂組成物をフィルム化(フィルム状に成形)することで得ることができる。前記樹脂組成物からなるフィルムは、1層でもよく、多層フィルムの様態としても使用できる。多層フィルムの積層構成としては、特に限定されるものではないが、例えば、本発明の一態様である樹脂組成物の層(I)のみだけでなく他の成分からなる層、例えばバージン樹脂層(II)、接着層(III)またはバリア層(IV)などを含んでいてもよい。具体的には、層(I)/層(II)、層(II)/層(I)/層(II)、層(I)/層(III)/層(IV)/層(III)/層(I)、層(I)/層(III)/層(IV)/層(III)/層(II)などが挙げられる。なお、層間の/は、層が隣接していることを意味している。前記樹脂組成物からなるフィルムの厚みは、特に限定されるものではないが、フィッシュアイの発生をより抑制する観点から、10μm~300μmであることが好ましい。 The film of one embodiment of the present invention can be obtained by forming the resin composition into a film (molding into a film shape). The film made of the resin composition may be a single layer or may be used in the form of a multilayer film. The lamination structure of the multilayer film is not particularly limited, but may include, for example, not only the layer (I) of the resin composition of one embodiment of the present invention but also layers made of other components, such as a virgin resin layer (II), an adhesive layer (III) or a barrier layer (IV). Specific examples include layer (I)/layer (II), layer (II)/layer (I)/layer (II), layer (I)/layer (III)/layer (IV)/layer (III)/layer (I), layer (I)/layer (III)/layer (IV)/layer (III)/layer (II), etc. The "/" between layers means that the layers are adjacent to each other. The thickness of the film made of the resin composition is not particularly limited, but is preferably 10 μm to 300 μm from the viewpoint of further suppressing the occurrence of fisheyes.

 フィルム成形温度は190℃以上250℃以下の範囲が好ましく、200℃以上250℃以下の範囲がより好ましく、220℃以上250℃以下の範囲がさらに好ましい。成形温度が190℃以上であればフィッシュアイの発生が少なく、250℃以下であればフィルム成形性に優れるため好ましい。 The film forming temperature is preferably in the range of 190°C to 250°C, more preferably in the range of 200°C to 250°C, and even more preferably in the range of 220°C to 250°C. A forming temperature of 190°C or higher is preferable because it reduces the occurrence of fish eyes, while a forming temperature of 250°C or lower is preferable because it provides excellent film formability.

 前記フィルムは、食品、日用品、工業部品、医薬品、事務用品、化学用品などの包装容器、表面保護フィルム、サイレージラップなどの農業用フィルム、シュリンクフィルム、輸送袋などとして有用である。 The film is useful as a packaging container for food, daily necessities, industrial parts, medicines, office supplies, chemical products, etc., a surface protection film, an agricultural film such as silage wrap, a shrink film, a transport bag, etc.

 〔まとめ〕
 すなわち、本発明の各態様は、以下の[1]~[15]である。
[1] 酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物(a1)を50質量部以上99質量部以下、スチレン系ブロック共重合体(a2)1質量部以上50質量部以下(ここで(a1)および(a2)の合計は100質量部とする)を含む樹脂組成物(A)。
[2] エチレン-酢酸ビニル共重合体を含む組成物(a1)に含まれる各エチレン-酢酸ビニル共重合体の酢酸ビニル含有量が6質量%以上90質量%以下である、[1]に記載の樹脂組成物(A)。
[3] エチレン-酢酸ビニル共重合体を含む組成物(a1)が、酢酸ビニル含有量の異なる3種以上のエチレン-酢酸ビニル共重合体を含む、[1]又は[2]に記載の樹脂組成物(A)。
[4] エチレン-酢酸ビニル共重合体組成物(a1)において、各エチレン-酢酸ビニル共重合体の酢酸ビニル含量の差が1質量%以上であり、さらに少なくとも一組のエチレン-酢酸ビニル共重合体の酢酸ビニル含量の差が40質量%以下である、[1]乃至[3]のいずれか一項に記載の樹脂組成物(A)。
[5] スチレン系ブロック共重合体(a2)がスチレン単量体単位を主体とする少なくとも1個の重合体ブロックと、共役ジエン化合物単量体単位を主体とする少なくとも1個の重合体ブロックを有しているブロック共重合体、またはこれらの水素添加物である、[1]乃至[4]のいずれか一項に記載の樹脂組成物(A)。
[6] スチレン系ブロック共重合体(a2)がスチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-イソプレン-スチレンブロック共重合体(SIS)またはこれらの水素添加物である、[1]乃至[5]のいずれか一項に記載の樹脂組成物(A)。
[7] スチレン系ブロック共重合体(a2)がスチレン-エチレン・ブチレン-スチレンブロック共重合体(SEBS)である、[1]乃至[6]のいずれか一項に記載の樹脂組成物(A)。
[8] スチレン-エチレン・ブチレン-スチレンブロック共重合体(SEBS)のスチレンブロック比率が10質量%以上50質量%以下である[7]に記載の樹脂組成物(A)。
[9] [1]乃至[8]いずれか一項に記載の樹脂組成物(A)を含む、樹脂相溶化剤。
[10] [1]乃至[8]いずれか一項に記載の樹脂組成物(A)と、ポリオレフィンおよびポリエステルを含む熱可塑性樹脂(B)を含み、熱可塑性樹脂(B)100質量部に対して、樹脂組成物(A)を1質量部以上15質量部以下含む、樹脂組成物。
[11] ポリエステルがポリエチレンテレフタレートである、[10]に記載の樹脂組成物。
[12] 熱可塑性樹脂(B)に含まれる樹脂がプラスチック廃棄物を回収して得られた樹脂である、[10]又は[11]に記載の樹脂組成物。
[13] [10]乃至[12]のいずれか一項に記載の樹脂組成物からなる成形体。
[14] [10]乃至[12]のいずれか一項に記載の樹脂組成物からなるフィルム。
[15] [14]に記載のフィルムからなる包装容器。
〔summary〕
That is, the respective aspects of the present invention are as follows [1] to [15].
[1] A resin composition (A) comprising 50 parts by mass or more and 99 parts by mass or less of a composition (a1) containing at least two kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents, and 1 part by mass or more and 50 parts by mass or less of a styrene-based block copolymer (a2) (wherein the total of (a1) and (a2) is 100 parts by mass).
[2] The resin composition (A) according to [1], wherein the vinyl acetate content of each ethylene-vinyl acetate copolymer contained in the composition (a1) containing an ethylene-vinyl acetate copolymer is 6% by mass or more and 90% by mass or less.
[3] The resin composition (A) according to [1] or [2], wherein the composition (a1) containing an ethylene-vinyl acetate copolymer contains three or more ethylene-vinyl acetate copolymers having different vinyl acetate contents.
[4] In the ethylene-vinyl acetate copolymer composition (a1), the difference in vinyl acetate content between each ethylene-vinyl acetate copolymer is 1 mass% or more, and further, the difference in vinyl acetate content between at least one pair of ethylene-vinyl acetate copolymers is 40 mass% or less. The resin composition (A) according to any one of [1] to [3].
[5] The resin composition (A) according to any one of [1] to [4], wherein the styrene-based block copolymer (a2) is a block copolymer having at least one polymer block mainly composed of styrene monomer units and at least one polymer block mainly composed of conjugated diene compound monomer units, or a hydrogenated product thereof.
[6] The resin composition (A) according to any one of [1] to [5], wherein the styrene-based block copolymer (a2) is a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), or a hydrogenated product thereof.
[7] The resin composition (A) according to any one of [1] to [6], wherein the styrene-based block copolymer (a2) is a styrene-ethylene-butylene-styrene block copolymer (SEBS).
[8] The resin composition (A) according to [7], wherein the styrene block ratio of the styrene-ethylene butylene-styrene block copolymer (SEBS) is 10% by mass or more and 50% by mass or less.
[9] A resin compatibilizer comprising the resin composition (A) according to any one of [1] to [8].
[10] A resin composition comprising the resin composition (A) according to any one of [1] to [8] and a thermoplastic resin (B) containing a polyolefin and a polyester, the resin composition (A) being contained in an amount of 1 part by mass or more and 15 parts by mass or less per 100 parts by mass of the thermoplastic resin (B).
[11] The resin composition according to [10], wherein the polyester is polyethylene terephthalate.
[12] The resin composition according to [10] or [11], wherein the resin contained in the thermoplastic resin (B) is a resin obtained by recovering plastic waste.
[13] A molded article made of the resin composition according to any one of [10] to [12].
[14] A film made of the resin composition according to any one of [10] to [12].
[15] A packaging container made of the film according to [14].

 以下、実施例および比較例により本発明を説明するが、本発明はこれらに限定されるものではない。 The present invention will be explained below with reference to examples and comparative examples, but the present invention is not limited to these.

 [評価方法]
(1)メルトマスフローレート(MFR)
 樹脂組成物、エチレン-酢酸ビニル共重合体のMFRは、メルトインデクサー(宝工業製)にて190℃、2.16kg荷重の条件にて測定した。
[Evaluation method]
(1) Melt Mass Flow Rate (MFR)
The MFR of the resin composition and the ethylene-vinyl acetate copolymer was measured using a melt indexer (manufactured by Takara Kogyo Co., Ltd.) at 190° C. and a load of 2.16 kg.

(2)フィッシュアイ数
 作製したフィルムの500cmあたりのフィッシュアイの数を目視でカウントした。
(2) Number of Fisheyes The number of fisheyes per 500 cm2 of the prepared film was visually counted.

(3)全光線透過率
 フィルムの透明性の指標として全光線透過率をヘーズメーター(日本電色工業製、NDH7000型)にて測定した。
(3) Total Light Transmittance As an index of film transparency, the total light transmittance was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., Model NDH7000).

(4)フィルムの表面平滑性
 フィルムの表面平滑性を目視で評価した。表面荒れが小さいものを○、表面荒れが大きいものを×とした。
(4) Surface Smoothness of Film The surface smoothness of the film was evaluated by visual inspection. Films with little surface roughness were marked with ◯, and films with much roughness were marked with ×.

 [実施例1]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた。
[Example 1]
As the resin composition (A), a resin composition having the following composition was used.

 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)2質量部
 ・酢酸ビニル含量50質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-50)(ランクセス(株)製 商品名レバプレン500)1質量部
 ・酢酸ビニル含量80質量%、メルトマスフローレート5.0g/10分であるエチレン-酢酸ビニル共重合体(a1-80)(ランクセス(株)製 商品名レバプレン800)1質量部
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-13)(KRATON製、スチレン含量13質量%、商品名G1657VS)1質量部
(Resin composition (A))
2 parts by mass of ethylene-vinyl acetate copolymer (a1-25) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Tosoh Corporation, product name Ultrathene 640) Vinyl acetate content 1 part by mass of ethylene-vinyl acetate copolymer (a1-50) (manufactured by LANXESS AG, product name Levaprene 500) having a vinyl acetate content of 80% by mass and a melt mass flow rate of 3.0 g/10 min 1 part by mass of ethylene-vinyl acetate copolymer (a1-80) (manufactured by LANXESS AG, product name Levaprene 800) having a mass flow rate of 5.0 g/10 min. Styrene-ethylene-butylene-styrene block copolymer (a2 -13) (KRATON, styrene content 13% by mass, product name G1657VS) 1 part by mass

 前記樹脂組成物をドライブレンドし、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度160℃、スクリュ回転数150rpmの条件で溶融混練し、樹脂組成物(A)のペレットを得た。 The resin composition was dry blended and melt-kneaded using a twin-screw extruder (manufactured by Technovel, product name ULT nano 25TW) with a screw diameter of 25 mm at a resin temperature of 160°C and a screw rotation speed of 150 rpm to obtain pellets of resin composition (A).

 また、少なくともポリオレフィンおよびポリエステルを含む熱可塑性樹脂(B)として下記の樹脂を用いた。 The following resin was used as the thermoplastic resin (B) containing at least polyolefin and polyester:

 (熱可塑性樹脂(B))
 ・直鎖状低密度ポリエチレン(東ソー製、MFR2.0g/10分、商品名ニポロンZ HF210K)90質量部
 ・ポリエチレンテレフタレート(ユニチカ製、商品名MA-2103)10質量部
(Thermoplastic resin (B))
Linear low-density polyethylene (manufactured by Tosoh, MFR 2.0 g/10 min, product name Nipolon Z HF210K) 90 parts by mass Polyethylene terephthalate (manufactured by Unitika, product name MA-2103) 10 parts by mass

 前記樹脂をドライブレンドし、熱可塑性樹脂(B)とした。 The above resins were dry blended to obtain thermoplastic resin (B).

 樹脂組成物(A)5質量部と熱可塑性樹脂(B)100質量部をタンブラー混合機で予備ブレンドした。次に、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度260℃、スクリュ回転数300rpmの条件で溶融混合した。溶融混合後、室温まで冷却することで樹脂組成物ペレット(溶融混合物)を得た。樹脂組成物のMFRは3.0g/10分であった。 Five parts by mass of resin composition (A) and 100 parts by mass of thermoplastic resin (B) were pre-blended in a tumbler mixer. Next, using a twin-screw extruder (manufactured by Technovel, product name ULT nano 25TW) with a screw diameter of 25 mm, the mixture was melt-mixed at a resin temperature of 260°C and a screw rotation speed of 300 rpm. After melt mixing, the mixture was cooled to room temperature to obtain resin composition pellets (molten mixture). The MFR of the resin composition was 3.0 g/10 min.

 マイクロキャスト成形機(Labtech Engineering製)を用い、前記樹脂組成物ペレットからなる単層フィルムを得た。 A single-layer film made of the resin composition pellets was obtained using a microcast molding machine (manufactured by Labtech Engineering).

 このとき、成形温度を200℃とし、引取速度2m/分でフィルム幅50mm、フィルムの総厚み50μmとした。 The molding temperature was 200°C, the take-up speed was 2 m/min, the film width was 50 mm, and the total film thickness was 50 μm.

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [実施例2]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Example 2]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.

 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)2質量部
 ・酢酸ビニル含量50質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-50)(ランクセス(株)製 商品名レバプレン500)1質量部
 ・酢酸ビニル含量80質量%、メルトマスフローレート5.0g/10分であるエチレン-酢酸ビニル共重合体(a1-80)(ランクセス(株)製 商品名レバプレン800)1質量部
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-30)(KRATON製、スチレン含量30質量%、商品名G1726MS)1質量部
(Resin composition (A))
2 parts by mass of ethylene-vinyl acetate copolymer (a1-25) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Tosoh Corporation, product name Ultrathene 640) Vinyl acetate content 1 part by mass of ethylene-vinyl acetate copolymer (a1-50) (manufactured by LANXESS AG, product name Levaprene 500) having a vinyl acetate content of 80% by mass and a melt mass flow rate of 3.0 g/10 min 1 part by mass of ethylene-vinyl acetate copolymer (a1-80) (manufactured by LANXESS AG, product name Levaprene 800) having a mass flow rate of 5.0 g/10 min. Styrene-ethylene-butylene-styrene block copolymer (a2 -30) (KRATON, styrene content 30% by mass, product name G1726MS) 1 part by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [実施例3]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)1.5質量部
 ・酢酸ビニル含量50質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-50)(ランクセス(株)製 商品名レバプレン500)0.75質量部
 ・酢酸ビニル含量80質量%、メルトマスフローレート5.0g/10分であるエチレン-酢酸ビニル共重合体(a1-80)(ランクセス(株)製 商品名レバプレン800)0.75質量部
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-30)(KRATON製、スチレン含量30質量%、商品名G1726MS)2質量部
[Example 3]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.
(Resin composition (A))
Ethylene-vinyl acetate copolymer (a1-25) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Tosoh Corporation, product name Ultrasen 640) 1.5 parts by mass Ethylene-vinyl acetate copolymer (a1-50) having a vinyl acetate content of 50% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Lanxess Co., Ltd., product name Levaprene 500) 0.75 parts by mass Ethylene-vinyl acetate copolymer (a1-80) having a vinyl acetate content of 80% by mass and a melt mass flow rate of 5.0 g/10 min (manufactured by Lanxess Co., Ltd., product name Levaprene 800) 0.75 parts by mass Styrene-ethylene butylene-styrene block copolymer (a2-30) (manufactured by KRATON, styrene content 30% by mass, product name G1726MS) 2 parts by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, total light transmittance, and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例1]
 少なくともポリオレフィンおよびポリエステルを含む熱可塑性樹脂(B)として、直鎖状低密度ポリエチレン(東ソー製、MFR2.0g/10分、商品名ニポロンZ HF210K)90質量部、ポリエチレンテレフタレート(ユニチカ製、商品名MA-2103)10質量部のドライブレンドで作製した複合樹脂を100質量部使用した以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Comparative Example 1]
A monolayer film was obtained in the same manner as in Example 1, except that 100 parts by mass of a composite resin prepared by dry blending 90 parts by mass of linear low-density polyethylene (manufactured by Tosoh, MFR 2.0 g/10 min, product name Nipolon Z HF210K) and 10 parts by mass of polyethylene terephthalate (manufactured by Unitika, product name MA-2103) was used as the thermoplastic resin (B) containing at least polyolefin and polyester. The MFR of the resin composition was 3.0 g/10 min.

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, total light transmittance, and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例2]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)5質量部
[Comparative Example 2]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.
(Resin composition (A))
5 parts by mass of ethylene-vinyl acetate copolymer (a1-25) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Tosoh Corporation, product name Ultrathene 640)

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例3]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Comparative Example 3]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.

 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)2.5質量部
 ・酢酸ビニル含量50質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-50)(ランクセス(株)製 商品名レバプレン500)1.25質量部
 ・酢酸ビニル含量80質量%、メルトマスフローレート5.0g/10分であるエチレン-酢酸ビニル共重合体(a1-80)(ランクセス(株)製 商品名レバプレン800)1.25質量部
(Resin composition (A))
2.5 parts by mass of ethylene-vinyl acetate copolymer (a1-25) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by Tosoh Corporation, product name Ultrathene 640) 1.25 parts by mass of ethylene-vinyl acetate copolymer (a1-50) having a vinyl content of 50% by mass and a melt mass flow rate of 3.0 g/10 min (manufactured by LANXESS AG, product name Levaprene 500) 1.25 parts by mass of ethylene-vinyl acetate copolymer (a1-80) (manufactured by LANXESS AG, product name Levaprene 800) having a melt mass flow rate of 5.0 g/10 min

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例4]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
 (樹脂組成物(A))
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-13)(KRATON製、スチレン含量13質量%、商品名G1657VS)5質量部
[Comparative Example 4]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.
(Resin composition (A))
Styrene-ethylene-butylene-styrene block copolymer (a2-13) (manufactured by KRATON, styrene content 13% by mass, product name G1657VS) 5 parts by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例5]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Comparative Example 5]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.

 (樹脂組成物(A))
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-30)(KRATON製、スチレン含量30質量%、商品名G1726MS)5質量部
(Resin composition (A))
Styrene-ethylene-butylene-styrene block copolymer (a2-30) (manufactured by KRATON, styrene content 30% by mass, product name G1726MS) 5 parts by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, total light transmittance, and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例6]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Comparative Example 6]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.

 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)4質量部
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-13)(KRATON製、スチレン含量13質量%、商品名G1657VS)1質量部
(Resin composition (A))
4 parts by mass of ethylene-vinyl acetate copolymer (a1-25) (product name Ultrathene 640, manufactured by Tosoh Corporation) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min. Styrene-ethylene Butylene-styrene block copolymer (a2-13) (manufactured by KRATON, styrene content 13% by mass, product name G1657VS) 1 part by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

 [比較例7]
 樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は実施例1と同様の手法により単層フィルムを得た。なお、樹脂組成物のMFRは3.0g/10分であった。
[Comparative Example 7]
A single layer film was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A). The MFR of the resin composition was 3.0 g/10 min.

 (樹脂組成物(A))
 ・酢酸ビニル含量25質量%、メルトマスフローレート3.0g/10分であるエチレン-酢酸ビニル共重合体(a1-25)(東ソー(株)製 商品名ウルトラセン640)4質量部
 ・スチレン-エチレン・ブチレン-スチレンブロック共重合体(a2-30)(KRATON製、スチレン含量30質量%、商品名G1726MS)1質量部
(Resin composition (A))
4 parts by mass of ethylene-vinyl acetate copolymer (a1-25) (product name Ultrathene 640, manufactured by Tosoh Corporation) having a vinyl acetate content of 25% by mass and a melt mass flow rate of 3.0 g/10 min. Styrene-ethylene Butylene-styrene block copolymer (a2-30) (manufactured by KRATON, styrene content 30% by mass, product name G1726MS) 1 part by mass

 得られたフィルムに発生したフィッシュアイの数および全光線透過率、フィルム表面平滑性について前記評価方法で測定した。評価の結果を表1に示す。 The number of fisheyes that occurred in the obtained film, as well as the total light transmittance and film surface smoothness were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

 表1に示すように、実施例1~3のフィルムは、フィッシュアイ数が2つ以下であり、フィッシュアイの発生の抑制が確認された。また、表面平滑性が良好であり、フィルム外観に優れることが確認された。 As shown in Table 1, the films of Examples 1 to 3 had two or less fisheyes, confirming that the occurrence of fisheyes was suppressed. In addition, it was confirmed that the surface smoothness was good and the film appearance was excellent.

 本発明の樹脂組成物からなるフィルムは、食品、日用品、工業部品、医薬品、事務用品、化学用品などの包装容器、表面保護フィルム、サイレージラップなどの農業用フィルム、シュリンクフィルム、輸送袋などとして有用である。 Films made from the resin composition of the present invention are useful as packaging containers for food, daily necessities, industrial parts, pharmaceuticals, office supplies, chemical products, etc., surface protection films, agricultural films such as silage wrap, shrink films, transport bags, etc.

Claims (15)

 酢酸ビニル含量が異なる少なくとも2種のエチレン-酢酸ビニル共重合体を含む組成物(a1)を50質量部以上99質量部以下、スチレン系ブロック共重合体(a2)1質量部以上50質量部以下(ここで(a1)および(a2)の合計は100質量部とする)を含む樹脂組成物(A)。 Resin composition (A) containing 50 parts by mass or more and 99 parts by mass or less of composition (a1) containing at least two types of ethylene-vinyl acetate copolymers with different vinyl acetate contents, and 1 part by mass or more and 50 parts by mass or less of styrene-based block copolymer (a2) (wherein the sum of (a1) and (a2) is 100 parts by mass).  エチレン-酢酸ビニル共重合体を含む組成物(a1)に含まれる各エチレン-酢酸ビニル共重合体の酢酸ビニル含有量が6質量%以上90質量%以下である、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, in which the vinyl acetate content of each ethylene-vinyl acetate copolymer contained in the composition (a1) containing an ethylene-vinyl acetate copolymer is 6% by mass or more and 90% by mass or less.  エチレン-酢酸ビニル共重合体を含む組成物(a1)が、酢酸ビニル含有量の異なる3種以上のエチレン-酢酸ビニル共重合体を含む、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, wherein the composition (a1) containing an ethylene-vinyl acetate copolymer contains three or more types of ethylene-vinyl acetate copolymers having different vinyl acetate contents.  エチレン-酢酸ビニル共重合体組成物(a1)において、各エチレン-酢酸ビニル共重合体の酢酸ビニル含量の差が1質量%以上であり、さらに少なくとも一組のエチレン-酢酸ビニル共重合体の酢酸ビニル含量の差が40質量%以下である、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, in which the difference in vinyl acetate content of each ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer composition (a1) is 1% by mass or more, and further the difference in vinyl acetate content of at least one pair of ethylene-vinyl acetate copolymers is 40% by mass or less.  スチレン系ブロック共重合体(a2)がスチレン単量体単位を主体とする少なくとも1個の重合体ブロックと、共役ジエン化合物単量体単位を主体とする少なくとも1個の重合体ブロックを有しているブロック共重合体、またはこれらの水素添加物である、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, wherein the styrene-based block copolymer (a2) is a block copolymer having at least one polymer block mainly composed of styrene monomer units and at least one polymer block mainly composed of conjugated diene compound monomer units, or a hydrogenated product thereof.  スチレン系ブロック共重合体(a2)がスチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-イソプレン-スチレンブロック共重合体(SIS)またはこれらの水素添加物である、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, wherein the styrene-based block copolymer (a2) is a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), or a hydrogenated product thereof.  スチレン系ブロック共重合体(a2)がスチレン-エチレン・ブチレン-スチレンブロック共重合体(SEBS)である、請求項1に記載の樹脂組成物(A)。 The resin composition (A) according to claim 1, wherein the styrene-based block copolymer (a2) is a styrene-ethylene-butylene-styrene block copolymer (SEBS).  スチレン-エチレン・ブチレン-スチレンブロック共重合体(SEBS)のスチレンブロック比率が10質量%以上50質量%以下である請求項7に記載の樹脂組成物(A)。 The resin composition (A) according to claim 7, in which the styrene block ratio of the styrene-ethylene-butylene-styrene block copolymer (SEBS) is 10% by mass or more and 50% by mass or less.  請求項1乃至8いずれか一項に記載の樹脂組成物(A)を含む、樹脂相溶化剤。 A resin compatibilizer comprising the resin composition (A) according to any one of claims 1 to 8.  請求項1に記載の樹脂組成物(A)と、ポリオレフィンおよびポリエステルを含む熱可塑性樹脂(B)を含み、
 熱可塑性樹脂(B)100質量部に対して、樹脂組成物(A)を1質量部以上15質量部以下含む、樹脂組成物。
A thermoplastic resin composition comprising the resin composition (A) according to claim 1 and a thermoplastic resin (B) containing a polyolefin and a polyester,
A resin composition comprising 1 part by mass or more and 15 parts by mass or less of a resin composition (A) relative to 100 parts by mass of a thermoplastic resin (B).
 ポリエステルがポリエチレンテレフタレートである、請求項10に記載の樹脂組成物。 The resin composition according to claim 10, wherein the polyester is polyethylene terephthalate.  熱可塑性樹脂(B)に含まれる樹脂がプラスチック廃棄物を回収して得られた樹脂である、請求項10に記載の樹脂組成物。 The resin composition according to claim 10, wherein the resin contained in the thermoplastic resin (B) is a resin obtained by recovering plastic waste.  請求項10乃至12のいずれか一項に記載の樹脂組成物からなる成形体。 A molded article made of the resin composition according to any one of claims 10 to 12.  請求項10乃至12のいずれか一項に記載の樹脂組成物からなるフィルム。 A film made of the resin composition according to any one of claims 10 to 12.  請求項14に記載のフィルムからなる包装容器。 A packaging container made of the film described in claim 14.
PCT/JP2024/009700 2023-03-27 2024-03-13 Resin composition, modifier, and composition containing said modifier Pending WO2024203319A1 (en)

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Citations (8)

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JPS6143656A (en) * 1984-08-08 1986-03-03 Kanebo Ltd Thermoplastic polyester resin
JPS62187758A (en) * 1986-02-14 1987-08-17 Kanebo Ltd thermoplastic resin composition
JP2002273841A (en) * 2001-03-16 2002-09-25 Hiraoka & Co Ltd Soft polyolefinic resin laminated sheet
JP2006089603A (en) * 2004-09-24 2006-04-06 Dainippon Ink & Chem Inc Resin composition for coating and insulated wire using the same
WO2007063973A1 (en) * 2005-11-30 2007-06-07 Mitsubishi Plastics, Inc. Thermally shrinkable polyolefin film, molded article using the film, thermally shrinkable label, and container
JP2019001163A (en) * 2017-06-16 2019-01-10 日東電工株式会社 Multilayer film, laminate, airbag, and method for producing laminate
JP2020158763A (en) * 2019-03-25 2020-10-01 東ソー株式会社 Resin composition and film for lid material
WO2021171190A1 (en) * 2020-02-25 2021-09-02 Dupont Teijin Films U.S. Limited Partnership Composite polymeric film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143656A (en) * 1984-08-08 1986-03-03 Kanebo Ltd Thermoplastic polyester resin
JPS62187758A (en) * 1986-02-14 1987-08-17 Kanebo Ltd thermoplastic resin composition
JP2002273841A (en) * 2001-03-16 2002-09-25 Hiraoka & Co Ltd Soft polyolefinic resin laminated sheet
JP2006089603A (en) * 2004-09-24 2006-04-06 Dainippon Ink & Chem Inc Resin composition for coating and insulated wire using the same
WO2007063973A1 (en) * 2005-11-30 2007-06-07 Mitsubishi Plastics, Inc. Thermally shrinkable polyolefin film, molded article using the film, thermally shrinkable label, and container
JP2019001163A (en) * 2017-06-16 2019-01-10 日東電工株式会社 Multilayer film, laminate, airbag, and method for producing laminate
JP2020158763A (en) * 2019-03-25 2020-10-01 東ソー株式会社 Resin composition and film for lid material
WO2021171190A1 (en) * 2020-02-25 2021-09-02 Dupont Teijin Films U.S. Limited Partnership Composite polymeric film

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