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WO2019180671A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2019180671A1
WO2019180671A1 PCT/IB2019/052336 IB2019052336W WO2019180671A1 WO 2019180671 A1 WO2019180671 A1 WO 2019180671A1 IB 2019052336 W IB2019052336 W IB 2019052336W WO 2019180671 A1 WO2019180671 A1 WO 2019180671A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
polyester
mass
polyethylene terephthalate
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2019/052336
Other languages
English (en)
Japanese (ja)
Inventor
太田匡彦
ジョン マキャフリィニコラス
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.)
Plantic Technologies Ltd
Original Assignee
Plantic Technologies Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Plantic Technologies Ltd filed Critical Plantic Technologies Ltd
Priority to JP2020508099A priority Critical patent/JP7246374B2/ja
Publication of WO2019180671A1 publication Critical patent/WO2019180671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention includes a resin composition in which polyester is dispersed in polyethylene terephthalate, a method for producing the same, a film composed of the resin composition, and a layer comprising the resin composition.
  • the present invention relates to a laminate and the resin composition or a container comprising the laminate.
  • PET polyethylene terephthalate
  • Patent Document 1 Japanese Patent Laid-Open No. 10-1 2 0 8 0 2
  • a resin composition used for such a transparent container or the like is required to have cutability and transparency that can suppress the occurrence of defects during cutting.
  • a conventional resin composition containing PET may not be able to satisfy both cut and transparency at the same time.
  • an object of the present invention includes a resin composition capable of achieving both excellent cutability and transparency, a method for producing the resin composition, a film composed of the resin composition, and the resin composition.
  • An object of the present invention is to provide a laminate comprising one or more layers, a resin composition or a container comprising the laminate.
  • polyester (8) contains structural units derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the content of polyester (8) is more than 0.1% by mass, and 3 If the average particle size in terms of the equivalent circle of polyester (8) is less than 0% by mass, it has been found that the above problems can be solved, and the present invention has been completed. That is, the present invention includes the following.
  • the content of the polyester () is more than 0.1% by mass and less than 30% by mass with respect to the mass of the resin composition
  • Polyester (8) dispersed in polyethylene terephthalate ( ⁇ ) has an average particle size equivalent to a circle of 5 obtained from a cross-sectional photograph taken with a scanning electron microscope.
  • a resin composition is provided.
  • the content of the structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol is 5 to 5 based on the total number of moles of all structural units derived from the diol contained in the polyester ().
  • the content of structural units derived from ethylene glycol contained in the polyethylene terephthalate ( ⁇ ) is 82 mol% or more based on the total amount of structural units derived from diol contained in the polyethylene terephthalate ( ⁇ ).
  • the resin composition according to any one of [1] to [3].
  • a laminate comprising 3 or more.
  • At least one of the layers included in the laminate is a gas barrier layer including a gas barrier material, and the oxygen permeability of the gas barrier layer is 20 ° C.
  • a container comprising the resin composition according to any one of [1] to [4], or the laminate according to [6] or [7].
  • the resin composition of the present invention can achieve both excellent cutting properties and transparency.
  • the polyester (8) is dispersed in the polyethylene terephthalate-aluminum (a).
  • Polyester (8) indicates a polymer having an ester bond as the main bond in the main chain, and mainly has a structural unit derived from dicarboxylic acid and a structural unit derived from diol.
  • derived structural unit may be simply referred to as “unit”.
  • a structural unit derived from dicarboxylic acid may be referred to as a dicarboxylic acid unit
  • a structural unit derived from diol may be referred to as a diol unit. is there.
  • examples of the dicarboxylic acid constituting the dicarboxylic acid unit include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid; cyclohexanedicarboxylic acid, norbornene Alicyclic dicarboxylic acids such as dicarboxylic acid and tricyclodecane dicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenylke ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • terephthalic acid and naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable from the viewpoint of heat resistance, stability, and productivity.
  • Dicarboxylic acid can be used individually or in combination of 2 or more types.
  • the content of terephthalic acid units is preferably 50 mol% or more with respect to the total number of moles of all structural units derived from dicarboxylic acid, 70 mol% The above is more preferable, 90 mol% or more is more preferable, and 95 mol% or more is particularly preferable.
  • the diol unit constituting the polyester (8) includes a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
  • polyester (eight) and polyethylene terephthalate— ⁇ ( ⁇ ) become incompatible, reducing the adhesive strength at the interface between them.
  • the in the resin composition of the present invention since such polyester (8) is dispersed in polyethylene terephthalate, it is easy to exhibit excellent cutting properties.
  • the term “cutting property” refers to the property of easily cutting the resin composition, and the improvement of the cutting property means that the resin composition is more easily cut. Further, the cut property can be measured by a known method, for example, the method of Examples.
  • the content of the unit is all of the diol-derived polyester (8) Preferably, it is 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less, preferably 5 mol% or more, more preferably 10 mol%, based on the total number of moles of the structural units. The mol% or more, more preferably 20 mol% or more.
  • Ding 1 ⁇ / 100 ⁇ 0 is in the above range, the cutting property is more likely to be improved.
  • the diols constituting diol units other than 1/100 ⁇ units are, for example, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, methyl Aliphatic diols such as pentanediol and diethylene glycol; cyclohexane dimethanol (eg, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol), norbornene dimethanol, And alicyclic diols such as tricyclodecane dimethanol; aromatic diols such as bisphenol compounds and hydroquinone compounds.
  • cyclohexane dimethanol such as 1,4-cyclohexane dimethanol is preferable from the viewpoint of heat resistance, stability, and productivity.
  • Diols can be used alone or in combination of two or more.
  • Polyester (8) may contain other structural units other than the dicarboxylic acid unit and the diol unit as long as the effects of the present invention are not impaired.
  • other structural units include hydroxycarboxylic acid units.
  • the hydroxycarboxylic acid constituting the hydroxycarboxylic acid unit include aliphatic hydroxycarboxylic acids such as 10-hydroxyoctadecanoic acid, lactic acid, hydroxyacrylic acid, 2-hydroxy-2-methylpropionic acid, and hydroxybutyric acid; Cycloaliphatic hydroxycarboxylic acids such as loxymethylcyclohexanecarboxylic acid, hydroxymethylnorbornene carboxylic acid, and hydroxymethyltricyclodecanecarboxylic acid; hydroxybenzoic acid, hydroxytoluic acid, hydroxysinaftoeic acid, 3- (hydroxyphenyl) propionic acid And aromatic hydroxycarboxylic acids such as hydroxyphenylacetic acid and 3-hydroxy-3-phenylpropionic
  • the ratio of dicarboxylic acid units to diol units is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and more preferably 2: 1. To 1: 2, particularly preferably 1: 1. ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the polyethylene terephthalate ( ⁇ ) contained in the resin composition of the present invention is a polyester mainly having a dicarboxylic acid unit mainly composed of terephthalic acid units and a diol unit mainly composed of ethylene glycol units.
  • the content of terephthalic acid units contained in polyethylene terephthalate ( ⁇ ) is preferably 70 mol% or more, more preferably 80 mol%, based on the total amount of dicarboxylic acid units contained in polyethylene terephthalate ( ⁇ ).
  • the content of the ethylene glycol unit contained in the polyethylene terephthalate ( ⁇ ) is preferably 70 mol% or more, more preferably 80 0, based on the total amount of diol units contained in the polyethylene terephthalate ( ⁇ ). Mol% or more, more preferably 82 mol% or more, even more preferably 90 mol% or more, particularly preferably 92 mol% or more, more particularly preferably 95 mol% or more, most preferably 9 mol% or more, preferably 100 mol% or less, more preferably 99.9 mol% or less, and even more preferably 99 mol% or less.
  • the content of the terephthalic acid unit and the ethylene glycol unit contained in the polyethylene terephthalate ( ⁇ ) is equal to or higher than the above lower limit value, the strength of the resin composition is easily improved, and the contents are each If it is below the upper limit of the value, the transparency of the resin composition is likely to be improved.
  • the total amount of terephthalic acid units and ethylene glycol units contained in polyethylene terephthalate ( ⁇ ) is preferably 70 mol% with respect to the total number of moles of all the structural units constituting polyethylene terephthalate ( ⁇ ). More preferably, 80 mol% or more, more preferably 90 mol% or more, still more preferably 91 mol% or more, particularly preferably 95 mol% or more, more particularly preferably 96 mol%. %, Preferably 100 mol% or less, more preferably 99.9 mol% or less, and even more preferably 99 mol% or less.
  • the total amount at the 7th position is not less than the above lower limit value, it is easy to improve the cutability of the resin composition, and if the content is not more than the above upper limit value, the transparency of the resin composition is improved. Cheap.
  • the polyethylene terephthalate ( ⁇ ) may contain a structural unit derived from a bifunctional compound other than the terephthalic acid unit and the ethylene glycol unit, if necessary.
  • the bifunctional compound unit include other dicarboxylic acid units, other diol units, and hydroxycarboxylic acid units.
  • the dicarboxylic acid constituting other dicarboxylic acid units include dicarboxylic acids other than terephthalic acid exemplified in the section of [Polyester (8)], and examples of diols constituting other diol units. Examples thereof include diols other than ethylene glycol exemplified in the section [Polyester (8)].
  • hydroxycarboxylic acid constituting the hydroxycarboxylic acid unit examples include hydroxycarboxylic acids exemplified in the section [Polyester (8)]. Among these, it is preferable to use isophthalic acid as another dicarboxylic acid from the viewpoint of easily improving the transparency and cutting property of the resin composition. Two functional compound units can be used alone or in combination of two or more.
  • the content of the bifunctional compound unit is preferably 30 mol% or less, more preferably 20 mol%, based on the total number of moles of all the structural units constituting the polyethylene terephthalate ( ⁇ ). In the following, it is more preferably 10 mol% or less, preferably 0 mol% or more, more preferably 0.1 mol% or more, and further preferably 1 mol% or more.
  • the content of the bifunctional compound unit is not less than the above lower limit value, the transparency of the resin composition can be easily improved, and when the content is not more than the above upper limit value, the resin composition can be cut. Easy to improve.
  • the ratio of the dicarboxylic acid unit to the diol unit is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1-1: 2, particularly preferably 1: 1
  • the polyester (8) has 2, 2, 4, 4-tetramethyl ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the polyester (eight) dispersed in polyethylene terephthalate ( ⁇ ) has an average particle diameter in terms of a circle equivalent to 50 to 80 0 0 n obtained from a cross-sectional photograph taken with a scanning electron microscope. Therefore, it is possible to achieve both excellent cut and transparency.
  • the content of the polyester (8) is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less. More preferably, it is 10% by mass or less, and particularly preferably 4% by mass or less.
  • the content of the polyester (eight) is not less than the above lower limit, the cutability of the resin composition is easily improved, and when the content is not more than the above upper limit, the transparency of the resin composition is improved. No damage.
  • polyester (8) dispersed in polyethylene terephthalate ( ⁇ ) has an average particle diameter in terms of a circle equivalent to 50 n obtained from a cross-sectional photograph taken with a scanning electron microscope. Or more, preferably 1 00 n or more, more preferably 2 0 0 n or more, 8 0 0 ⁇ or less, preferably 7 0 0 n or less, more preferably Or less, more preferably
  • the average particle diameter in terms of yen is equal to or greater than the above lower limit, the cutability of the resin composition is easily improved, and when the average particle diameter is equal to or smaller than the upper limit, the transparency of the resin composition is improved. Easy to improve.
  • the average particle diameter in terms of yen can be calculated by, for example, measuring by the method described in the examples.
  • the absolute value of the difference between the refractive index of the polyethylene terephthalate ( ⁇ ) and the refractive index of the polyester (8) is preferably ⁇ .
  • the lower limit of the absolute value of the difference between the refractive index of the polyethylene terephthalate ( ⁇ ) and the refractive index of the polyester (8) is usually not less than 0.01.
  • the refractive index is specified in ⁇ 3 0 4 8 9 using an Abbe refractometer. ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the resin composition of the present invention may contain additives other than the polyester (8) and the polyethylene terephthalate ( ⁇ ) as long as the effects of the present invention are not impaired.
  • additives are not particularly limited, and other thermoplastic resins, fillers, processing stabilizers, weathering stabilizers, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, difficulty Examples include flame retardants, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, and preservatives.
  • thermoplastic resins include, for example, polyester resins other than the polyester (8) and polyethylene terephthalate ( ⁇ ), olefin resins, halogen-containing vinyl resins, polycarbonate resins, polythiocarbonate resins, polyacetal resins. Resins, polyamide resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, thermoplastic elastomers, and the like.
  • the content of the additive may be, for example, from 0 to 10% by mass with respect to the mass of the resin composition.
  • the resin composition of the present invention has a relatively low haze and excellent transparency.
  • the haze of the resin composition of the present invention is preferably 20% or less, more preferably 10% or less, still more preferably 7% or less, and particularly preferably 5% or less.
  • the lower limit of haze is usually 0% or more. The haze can be measured by the method described in the examples.
  • the present invention includes a film (or sheet) composed of the resin composition.
  • the thickness of the film (or sheet) is, for example, 5 to 1000, preferably 10 to 80, and more preferably 50 to 500.
  • the resin composition of the present invention can also be used in the form of pellets.
  • the resin composition of the present invention is to obtaining a mixed compound by mixing at least the port Riesuteru (eight) and the polyethylene terephthalate (snake)
  • Step I) is a step of mixing at least the polyester (8) and the polyethylene terephthalate ( ⁇ ), and the other additives and the like can be optionally mixed together.
  • Step (_0 is usually carried out using an extruder.
  • each component is subjected to shear stress by a screw, and is uniformly mixed while being heated by applying external heat to the barrel.
  • an ordinary single-screw extruder or twin-screw extruder can be used as the extruder in the present invention.
  • Ratio of screw diameter, extruder length (! _) And screw diameter (0)! -/ 0 ratio and the rotation speed of the screw can disperse polyester (8) in polyethylene terephthalate ( ⁇ ) and adjust the average particle diameter of polyester (eight) equivalent to 50 to 800 n It is appropriately selected within the range.
  • ⁇ polyethylene terephthalate
  • the twin screw extruder may be either co-rotating or counter-rotating.
  • the screw diameter is preferably !
  • the __ / 0 ratio is preferably 20 to 50.
  • the rotational speed of the screw is preferably 30 “0” or more, more preferably 50 “” or more, more preferably 8 0 “111” or more, particularly preferably 10 “0” or more, preferably 1 90 “ Or less, more preferably 180 or less.
  • the screw rotation speed is in the above range, it is easy to adjust the average particle diameter of polyester (eight) equivalent to the circle to the range of 50 to 80, It is easy to obtain a resin composition excellent in transparency and cutting property
  • the kneading temperature is, for example, 250 to 300 °
  • the kneading time is, for example, 20 seconds to 5 minutes.
  • Each component may be introduced directly into the extruder, and each component is extruded as a premix using a conventional mixer such as a Brabender, an open mouthl, a seconder, or a tumbler mixer. It may be introduced into the machine.
  • Step (I) is a step of extruding the mixture obtained in step I).
  • the molten mixture that has been pushed through the extruder while being melt-kneaded is removed.
  • the temperature of the die is preferably 2500-300 ° , more preferably 2600-285 °.
  • the mixture in the form of a film or a strand. Then, by cooling the extruded mixture, a film or strand resin composition is obtained.
  • the mixture When the mixture is extruded into a film, the mixture can be extruded from a film-forming die and then taken off while being cooled with a take-up roller. It is preferred to cool between the die and the mouth-raiser to prevent the mixture from sticking to the mouthler.
  • dehumidified air can be used to expand the film as the film exits the die.
  • Talc can also be entrained in the air stream to prevent film blocking.
  • the strand When the mixture is extruded into a strand shape, the strand can be formed into a pellet by extruding from a strand nozzle having a plurality of holes, cooling in a water bath, and cutting with a rotary cutter.
  • the moisture on the surface of the pellet can be removed with hot air, dehumidified air or an infrared heater by periodically or constantly applying vibration.
  • the known resin composition comprising polyethylene phthalate (Kenting) or the like is not sufficiently cool, it must be improved in crystallinity and orientation by a method such as stretching at least a specific stretching ratio. For example, when cutting, a fracture failure such as elongation of the cut portion occurs. On the other hand, since the resin composition of the present invention can exhibit excellent cutting properties without being stretched, productivity can be improved.
  • the present invention includes a laminate comprising one or more layers comprising the resin composition (hereinafter sometimes referred to as resin layer ( ⁇ )). That is, the resin composition of the present invention may be a single layer or a laminate (multilayer). In the case of a laminate, it may be composed entirely of the resin layer ( ⁇ ) or may be composed of the resin layer ( ⁇ ) and other layers. As the other layers, a layer with high transparency and cut property can be appropriately selected. For example, polyethylene terephthalate (Kenting), biaxially oriented polypropylene ( ⁇ ⁇ ), low density polyethylene (1_0 0), polylactic acid ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • At least one of the layers included in the laminate is a gas barrier layer, and more preferably, the gas barrier layer is provided on at least one surface of the resin layer ( ⁇ ).
  • the gas barrier layer may be laminated or bonded to the resin layer ( ⁇ ) through the adhesive layer.
  • the laminate of the present invention has a resin layer ( ⁇ ) / adhesive layer / gas barrier layer / adhesive layer / resin layer ( ⁇ ) in this order.
  • the kind of the resin composition which comprises each resin layer ( ⁇ ) may be the same or different.
  • the gas barrier layer comprises a gas barrier material.
  • the gas barrier material is not particularly limited as long as the obtained gas barrier layer has a high cut and transparency, and can exhibit gas barrier performance.
  • the gas barrier material preferably contains an ethylene-vinyl alcohol copolymer (mouth).
  • starch and / or modified starch ( ⁇ 3) is used as component (X, ethylene-vinyl alcohol copolymer (mouth) as component (mouth), and water-soluble resin ( ⁇ ) described later as component ( Sometimes referred to as i).
  • starch examples include starches derived from corn, cassava, potato, sweet potato, sago, evening pioca, sorghum, beans, bracken, lotus, bean sprout, wheat, rice, shrimp noodles, kuzu turmeric, peas and the like.
  • starch derived from corn and cassava is preferable, and starch derived from high amylose corn is more preferable.
  • Starch can be used alone or in combination of two or more.
  • Modified starch includes physically modified starch (eg starch, fractionated ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • Amylose, heat-moisture-treated starch, etc. Enzyme-modified starch (eg hydrolyzed dextrin, enzyme-degraded dextrin, amylose, etc.), chemically-degraded modified starch (eg acid-treated starch, hypochlorous acid-oxidized starch, dialdehyde denpen, etc.) ), Chemically modified starch derivatives (eg etherified starch, esterified starch, cationized starch, cross-linked starch, etc.).
  • the modified starch can be used alone or in combination of two or more.
  • etherified starch includes alkyl etherified starch (such as methyl etherified starch), carboxyalkyl etherified starch (such as carboxymethyl etherified starch), hydroxyalkyl etherified starch, and the like.
  • alkyl etherified starch such as methyl etherified starch
  • carboxyalkyl etherified starch such as carboxymethyl etherified starch
  • hydroxyalkyl etherified starch and the like.
  • etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms can be used.
  • the esterified starch may have other structural units, for example, a structural unit derived from a carboxylic acid such as acetic acid; a structural unit derived from maleic anhydride, a structural unit derived from phthalic anhydride, Examples include esterified starch having a structural unit derived from dicarboxylic acid anhydride such as a structural unit derived from octenyl succinic anhydride, and esterified starch having a structural unit derived from oxo acid such as nitric acid, phosphoric acid, and urea phosphoric acid. I can get lost.
  • Other examples include xanthate esterified starch and acetoacetate esterified starch.
  • Examples of the cationized starch include a reaction product of starch and 2-diethylaminoethyl chloride, a reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, and the like.
  • crosslinked starch examples include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, acrolein crosslinked starch and the like.
  • the modified starch is preferably an etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms, an esterified starch having a structural unit derived from a dicarboxylic anhydride, or a combination thereof. Hydroxye ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms may be obtained, for example, by a reaction between an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide with starch.
  • the average number of hydroxy groups used for modification is preferably from 0.005 to 2 per glucounit in starch.
  • Unmodified starch is preferred from the viewpoint of biodegradability, but unmodified starch is limited in optical transparency, moldability, tensile elasticity, etc. of the gas barrier layer due to aging. For this reason, it is preferred to include modified starches that improve these properties.
  • the content of the modified starch is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 10%, based on the total mass of the components ( ⁇ 3). 0% by mass.
  • Starch and / or modified starch ( ⁇ is a component ( ⁇ content of amylose is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. When the amylose content is 50% by mass or more, it is advantageous in terms of processability, while starch and / or modified starch ( ⁇ ) usually has an amylose content of 90% by mass or less. It is.
  • Ingredients (commercially available as ⁇ can be used.
  • Examples of typical commercially available products include, for example, ⁇ 1 ⁇ ! 9 “ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Hydroxypropyl etherified starch available from the company (Registered trademark), and I ⁇ n 3 I 7 (registered trademark) ⁇ ⁇ 1_ ⁇ 3 ⁇ (registered trademark) 8 9 3 9
  • the content of the component (O) is preferably 20 to 100 mass% with respect to the mass of the gas barrier material.
  • Ethylene-vinyl alcohol copolymer (mouth) [Snake Rei_1 ⁇ 1 (0)] is a copolymer having the ethylene Len units and vinyl alcohol units.
  • Snake Rei_1 ⁇ 1 (0) for example, can be a copolymer comprising ethylene and vinyl esters, obtained by saponification using an alkali catalyst or the like.
  • vinyl esters include vinyl acetate and fatty acid vinyl esters (such as vinyl propionate and vinyl bivalate).
  • EV0H (0) can contain, for example, a vinylsilane compound as a copolymerization component.
  • a vinylsilane compound examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (/ 3-methoxyethoxy) silane, and armethacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane can be preferably used.
  • Snake Rei_1 ⁇ 1 (0) to the extent that the purpose is not hindered in the present invention, other copolymerizable components, e.g., propylene, heptylene, (meth) acrylic acid, (meth) unsaturated methyl acrylate Carboxylic acid or its ester; 1 ⁇ 1-vinylpyrrolidone such as vinylpyrrolidone can be contained.
  • Snake Rei_1 ⁇ 1 (0) can be used alone or in combination of two or more.
  • the ethylene unit content is preferably 2 to 60 mol%, more preferably 10 to 50 mol%, and further 20 to 40 mol%. It is.
  • the oxygen permeability As the ethylene unit content becomes smaller, the oxygen permeability (Oc [3 ⁇ 4) tends to be reduced.
  • an oxygen barrier property is improved means that the oxygen permeability (0- [3]) is reduced, and an excellent oxygen barrier property means that the oxygen permeability is low.
  • saponification degree of vinyl alcohol units is a 9 0 mol% or more, preferably 9 5 mol% or more, more preferably 9 9 mol% More preferably, it is 99.5 mol% or more.
  • saponification degree is vinylal ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the content of the component (mouth) is preferably 5 to 100 mass% with respect to the mass of the gas barrier material.
  • the gas barrier material can further contain a water-soluble resin (i).
  • Resin having a water-soluble (Snake) are different resin from the snake Rei_1 ⁇ 1 (0) is a resin with a compatible component ( ⁇ ).
  • the water-soluble resin ( ⁇ ) preferably has a melting point suitable for the processing temperature of the component ( ⁇ ), and polyvinyl alcohol is preferred from the viewpoints of excellent moldability and good elastic modulus.
  • Polyvinyl alcohol is produced, for example, by hydrolysis of polyvinyl acetate obtained by polymerization of vinyl acetate monomer.
  • the saponification degree of polyvinyl alcohol is preferably 80 to 99.9 mol% from the viewpoint of sufficient strength and gas barrier properties.
  • the degree of saponification is more preferably 85 mol% or more, and still more preferably 88 mol% or more.
  • the degree of saponification refers to the mole fraction of hydroxyl groups relative to the total of hydroxyl groups and ester groups in polyvinyl alcohol.
  • the polyvinyl alcohol may further contain other monomer units other than the vinyl alcohol unit. And monomer units derived from ethylenically unsaturated monomers.
  • ethylenically unsaturated monomer include ⁇ -olefins such as propylene, n-butene, isoptylene, 1-hexene; acrylic acid and its salt; unsaturated monomer having an acrylate group; methacrylic acid and its Salt; unsaturated monomer having methacrylic acid ester group; acrylic amide, 1 ⁇ 1-methylacrylamide, 1 ⁇ 1_ethylacrylamide, 1 ⁇ 1, 1 ⁇ 1_dimethylacrylamide, Diacetone acrylamide, acrylamide propanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt (eg quaternary salt); methacrylamide, 1 ⁇ 1-methylmethacrylamide, 1 ⁇ 1-ethylmethacrylate Krillamide, methacrylamide propanesul
  • 3-Diacetoxy _ 1 -Allyl compounds such as allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and their salts or esters; vinylsilyl compounds such as vinyltrimethoxysilane; isopropyl acetate Nyl; sacrificial vinyl, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl bivalate, vinyl versatate, vinyl carboxylate, vinyl carlylate, vinyl laurate, vinyl palmitate, vinyl stearate, olein And vinyl ester monomers such as vinyl acid vinyl and vinyl benzoate.
  • unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and their salts or esters
  • vinylsilyl compounds such as vinyltrimethoxysilane
  • isopropyl acetate Nyl sacrificial vinyl, vinyl acetate, vinyl propionate,
  • monomer units derived from unsaturated monomers that have not been saponified are also included in the other monomer units.
  • the content of other monomer units is preferably 10 mol% or less, and more preferably 5 mol% or less.
  • the water-soluble resin ( ⁇ ) can be used alone or in combination of two or more.
  • the method for producing polyvinyl alcohol is not particularly limited. As described above, for example, a vinyl acetate monomer and, if necessary, another monomer are copolymerized, and the obtained copolymer is saponified. A method of converting to vinyl alcohol units is mentioned.
  • Examples of the polymerization method for copolymerization include batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization.
  • Examples of the polymerization method include known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
  • a known method can be applied to saponification of the copolymer. For example, it can be performed in a state where the copolymer is dissolved in alcohol or hydrous alcohol. Alcohol that can be used at this time ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • 18 is, for example, a lower alcohol such as methanol or ethanol.
  • the content of the component ( ⁇ ) is preferably 1 to 50 mass% with respect to the mass of the gas barrier material.
  • the gas barrier material may further contain a fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof.
  • fatty acids having 12 to 22 carbon atoms and fatty acid salts thereof include stearic acid, calcium stearate, sodium stearate, palmitic acid, lauric acid, myristic acid, linolenic acid, and behenic acid. .
  • stearic acid, calcium stearate, and sodium stearate are preferred from the viewpoint of processability.
  • Fatty acids having 12 to 22 carbon atoms and fatty acid salts thereof can be used alone or in combination of two or more.
  • the content in the gas barrier material is based on the mass of the gas barrier material. Preferably it is 0. 1-3 mass%, More preferably, it is 0. 03-2 mass%, More preferably, it is 0.1-1 mass%.
  • the content of the fatty acid having 12 to 22 carbon atoms and / or the fatty acid salt thereof is within the above range, it is advantageous in terms of additivity.
  • the gas barrier material may further contain layered silicate clay.
  • Layered silicate clays include synthetic or natural layered silicate clays such as montmorillonite, bentonite, bidelite, mica (mica), hectrite, saponite, nontronite, soconite, vermiculite, remnants. Dickite, magadite, kenyanite, stevensite, vorconscoite and mixtures thereof. Layered silicate clays can be used alone or in combination of two or more.
  • the content in the gas barrier material is preferably 0.1 to 5% by mass, more preferably ⁇ based on the mass of the gas barrier material. 1 to 3% by mass, more preferably 0.5 to 2% by mass.
  • transparency and ⁇ ⁇ 02019/180671 ⁇ (: 17132019/052336
  • the gas barrier material may further contain a plasticizer from the viewpoint of film formability.
  • plasticizers include water, sorbitol, glycerol, multi-ole, xylitol, mannitol, glycerol trioleate, epoxidized linseed oil, epoxidized soybean oil, tributyl citrate, acetyl triethyl citrate, and glyceryl triacetate. 2, 2, 4-trimethyl-1,3-pentanediol diisoptylate, polyethylene oxide, and polyethylene glycol.
  • Plasticizers can be used alone or in combination of two or more
  • the content of the plasticizer is preferably 0.1% by mass, more preferably 1% by mass as a lower limit with respect to the mass of the gas barrier material, from the viewpoint of the film-forming property and oxygen barrier property of the gas barrier material. More preferably, 10% by mass, particularly preferably 15% by mass, most preferably 20% by mass, and the upper limit is preferably 50% by mass, more preferably 45% by mass, still more preferably 40% by mass. .
  • the gas barrier material contains, as necessary, those exemplified as additives other than the polyester (8) and polyethylene terephthalate ( ⁇ ) described in the section [Resin composition]. Good.
  • the gas barrier layer comprising the gas barrier material is excellent in oxygen barrier properties.
  • the oxygen permeability of the gas barrier layer is preferably 10.00 at a temperature of 20 ° 0 and a relative humidity of 65%. 81: 111. ⁇ 13 or less, more preferable
  • the gas barrier layer can exhibit sufficient oxygen barrier properties.
  • the thickness of the gas barrier layer is, for example, 1 to 1 000, preferably 2 to 500, more preferably 5 to 200, from the viewpoint of the cutability of the obtained laminate.
  • the gas barrier layer comprising the gas barrier material comprises a step of mixing the components constituting the gas barrier material to obtain a mixture (3) ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the component constituting the gas barrier material for example, at least the component ( ⁇ and / or the component (mouth)) is mixed, and optionally the component ( ⁇ ) and the number of carbon atoms is 1 2 to 22 fatty acids and / or fatty acid salts thereof, the layered silicate clay, the plasticizer, and the other additives may be mixed together.
  • Step (3) is usually performed using an extruder.
  • shear stress is applied to each component with a screw, and they are mixed homogeneously while being heated by applying external heat to the barrel.
  • twin-screw extruder As the extruder, a twin-screw extruder can be used.
  • the twin screw extruder may be either co-rotating or counter-rotating. Screw diameter,!
  • the __ / 0 ratio and the screw rotation speed can be selected from the same ranges as those described in the section [Resin composition].
  • the lower limit is preferably 0.1% by mass, more preferably 1% by mass with respect to the mass of the gas barrier material. More preferably, 10% by mass, particularly preferably 15% by mass, most preferably 20% by mass, and the upper limit is preferably 50% by mass, more preferably 45% by mass, still more preferably 40% by mass.
  • % Plasticizer preferably further mixed with water.
  • the mass of the mixture represents the total mass of the mixture containing the plasticizer.
  • a plasticizer may be introduced into the initial stage of extrusion, and the plasticizer can be introduced before reaching the heating temperature, for example, at a temperature of 100 ° C. or less.
  • Starch and / or modified starch ( ⁇ is cooked by a combination of moisture, heat and shear stress, and can be gelatinized.
  • a plasticizer preferably water must be introduced separately.
  • the water-soluble polymer such as the water-soluble resin (i) can be dissolved, the gas barrier material can be softened, and the modulus and brittleness can be reduced.
  • step (3) preferably more than 100 °° and less than 150 °°, more preferably ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the cooking process is a process of crushing the starch granules and gelling. Heating can be performed by applying heat from the outside to the barrel of the extruder. Each barrel can be heated to the desired temperature by applying a stepwise change in temperature. 1 2 0 ° When cooking is performed at a temperature higher than 0 ° , it is advantageous in terms of workability.
  • the cooked mixture is preferably 8 5 to 1 in order to prevent foaming.
  • the residence time in the extruder can be set according to the temperature profile and the screw speed, and is preferably 1 to 2.5 minutes.
  • the molten mixture that has been pushed through the extruder while being melt-kneaded is extruded from a die.
  • the temperature of the die is preferably 85 to 120 °, more preferably 90 to 110 °.
  • the mixture in the form of a film.
  • a gas barrier layer containing a gas barrier material is obtained by cooling and drying the extruded mixture (melt).
  • the resin layer ( ⁇ ) and a layer other than the resin layer ( ⁇ ), preferably a gas barrier layer are bonded by a conventional method such as dry lamination. Can be obtained.
  • a laminate having a resin layer ( ⁇ ) / adhesive layer / gas barrier layer in this order by bonding a gas barrier layer to one or both sides of the resin layer ( ⁇ ) via an adhesive layer.
  • a laminate having a resin layer ( ⁇ ) / adhesive layer / gas barrier layer / adhesive layer / resin layer ( ⁇ ) in this order is obtained.
  • the laminate may be produced by co-extrusion molding or co-injection molding of the resin composition and the gas barrier material.
  • the present invention includes a container comprising the resin composition or the laminate.
  • the cut surface is extended. ⁇ ⁇ 0 2019/180671 ⁇ (: 17132019/052336
  • the resin composition or the laminate can be easily and simply cut into a predetermined shape and used in a container molding process.
  • the laminate of the present invention includes the gas barrier layer, gas barrier properties such as oxygen barrier properties can be imparted to the container. Therefore, the container of the present invention can be suitably used particularly for food packaging.
  • Examples of the cutting method include a method of cutting with a shearing force such as a punch cutter and a mouth-tally cutter, and a method using a sharp blade such as a crash cutter.
  • the present invention is effective in mechanical cutting including both. .
  • the image analysis Seo oice (1 ⁇ / 1_Rei 11 1 ⁇ 1 Chomi ⁇ 1 to 1 company Ltd., )
  • the entire contour is shown in the photo screen (the contour is not broken).
  • Each cross-sectional area was calculated for 50 parallel cross-sections, a total of 100 cross-sections. If there were less than 50 images in a single field of view, the field of view was expanded in a direction parallel to the film surface until 50. Note that the image analysis software automatically recognizes the particle outline. ⁇ ⁇ 02019/180671 ⁇ (: 17132019/052336
  • Thousand _ 74 isophthalic acid ( ⁇ eight; 2 mol% based on the total dicarboxylic acid unit) modified polyethylene terephthalate, 1_ ⁇ felling of trees snake Rei_1 ⁇ 1 Snake 1 ⁇ / 1 1 ⁇ eight 1_ Inc. Obtain from
  • T ritan TX 1 001 2, 2, 4, 4-Tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylene dimethylene) terephthalate, available from Eastman Chemical Company
  • T ritan TX 1 800 2, 2, 4, 4-Tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylene dimethylene) terephthalate, available from Eastman Chemical Company
  • Tritan TX 2001 2, 2 , 4, 4-Tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylene dimethylene) terephthalate, available from Eastman Chemical Company E aster 6763: 1,4-cyclohexanedimethanol Modified polyethylene terephthalate, obtained from Eastman Chemical Company
  • E aster AN 004 Poly (1,4-cyclohexylenedimethylene) terephthalate, obtained from Eastman Chemical Company
  • the take-out speed was set so that the extruded film had a predetermined thickness after cooling, and a film having a thickness of 1550 Mm was obtained.
  • the twin-screw extruder was operated by the co-rotation (meshing self-wiping) method.
  • a film of 150 was obtained in the same manner as in Example 1 except that Tritan 1X2001 was used as the polyester (eight).
  • a film of 150 was obtained in the same manner as in Example 1 except that 59) was used.
  • Example 509 was used in the same manner as in Example 1 except that 150 films were obtained.
  • a film of 1500 001 was obtained in the same manner as in Example 1 except that the rotational speed of the twin-screw extruder was set to 1 80 “.
  • a film of 1500 001 was obtained in the same manner as in Example 1 except that the rotation speed of the twin screw extruder was set to 50 ".
  • Example 1 Except that the rotation speed of the extruder was 200 rpm, the same as Example 1 was performed. I got a film.
  • polyester (A) except that Easter 6763 was used, the same as in Example 1 I got a film.
  • Example 1 Except for using Easter AN 004 as the polyester (A), the same as in Example 1 I got a film.
  • Table 1 shows the results of the average particle diameter, haze, and cutability of the films obtained in Examples 1 to 8 and Comparative Examples 1 to 8 in terms of a circle equivalent.
  • CH DM copolymerization amount (mol%) is the content of constituent units derived from 1,4-cyclohexanedimethanol (CH DM) with respect to the total number of moles of diol units contained in polyester (A).
  • the amount of TMCBD copolymerization (mol%) is that of the structural unit derived from 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol (TMCBD) with respect to the total number of moles of diol units contained in polyester (A).
  • TMCBD 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol
  • the content (% by mass) is the polyester to the mass of the resin composition ( ⁇ ⁇ 0 2019/180671 ⁇ (: 17162019/052336
  • ⁇ 0 copolymerization amount indicates the content of structural units derived from ethylene glycol ( ⁇ ⁇ ) relative to the total number of moles of diol units contained in polyethylene terephthalate ( ⁇ ).
  • the resin compositions obtained in Examples 1 to 8 have low haze and good cut evaluation. That is, the resin compositions obtained in Examples 1 to 8 can achieve both excellent cut property and transparency. On the other hand, the resin compositions obtained in Comparative Examples 1, 2, and 4 to 7 have poor cutability evaluation. Further, the resin composition obtained in Comparative Example 3 has high haze and low transparency. Therefore, the film made of the resin composition obtained in Comparative Examples 1 to 8 cannot achieve both cut and transparency.

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Abstract

La présente invention concerne une composition de résine dans laquelle un polyester (A) comprenant un motif structural dérivé du 2,2,4,4-tétraméthyl-1,3-cyclobutanediol est dispersé dans un polyéthylène téréphtalate (B). La teneur du polyester (A) est supérieure à 0,1 % en masse et inférieure à 30 % en masse de la masse de la composition de résine, et le polyester (A) dispersé dans le polyéthylène téréphtalate (B) possède un diamètre moyen de cercle équivalent des particules compris entre 50 et 800 nm tel qu'obtenu à partir d'une prise de vues en coupe transversale au moyen d'un microscope électronique à balayage.
PCT/IB2019/052336 2018-03-23 2019-03-22 Composition de résine Ceased WO2019180671A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12351711B2 (en) 2019-02-28 2025-07-08 Plantic Technologies Limited Starch compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263364A (en) * 1979-12-14 1981-04-21 Eastman Kodak Company Stampable reinforced thermoplastic polyester sheets
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