WO2011096395A1 - Procédé de fabrication d'un article étiré-moulé multicouche - Google Patents

Procédé de fabrication d'un article étiré-moulé multicouche Download PDF

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Publication number
WO2011096395A1
WO2011096395A1 PCT/JP2011/052034 JP2011052034W WO2011096395A1 WO 2011096395 A1 WO2011096395 A1 WO 2011096395A1 JP 2011052034 W JP2011052034 W JP 2011052034W WO 2011096395 A1 WO2011096395 A1 WO 2011096395A1
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Prior art keywords
resin
layer
pga
resin layer
molded product
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PCT/JP2011/052034
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English (en)
Japanese (ja)
Inventor
義紀 鈴木
盛昭 新崎
浩幸 佐藤
良 加藤
智 鈴木
慎弥 高橋
卓 佐藤
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株式会社クレハ
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Priority to JP2011552785A priority Critical patent/JPWO2011096395A1/ja
Publication of WO2011096395A1 publication Critical patent/WO2011096395A1/fr

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    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • 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
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • 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
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3032—Preforms or parisons made of several components having components being injected
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the present invention relates to a method for producing a multilayer stretch molded product, and more particularly, to a method for producing a multilayer stretch molded product including a layer containing a polyglycolic acid resin and a layer containing another thermoplastic resin.
  • Polyglycolic acid is attracting attention as a biodegradable polymer material with a low environmental impact because it is excellent in microbial degradability and hydrolyzability. Polyglycolic acid is also excellent in gas barrier properties, heat resistance, and mechanical strength. However, although such a polyglycolic acid film is excellent in mechanical strength, it is not necessarily sufficient for use as a polyglycolic acid monolayer, and is not sufficient in moisture resistance and economy. There wasn't. For this reason, the polyglycolic acid layer is usually used in combination with other resin layers in multiple layers.
  • the polyglycolic acid resin has high crystallinity and is easy to crystallize before stretch molding. When stretched, there was a problem that rupture or breakage occurred or a stretch group was likely to occur.
  • Patent Document 1 discloses that a laminate including a polyglycolic acid layer is thermoformed and cooled, and then made opaque. Until then, the polyglycolic acid layer is reheated and crystallized, and then a method for producing a multilayer stretch molded product is proposed in which the laminate is stretched.
  • the polyglycolic acid layer is reheated at a relatively high temperature of 80 to 200 ° C. until it becomes opaque, thereby forming a uniform crystal state.
  • a multilayer stretched molded article having excellent gas barrier properties and transparency is obtained.
  • since it reheats at comparatively high temperature there exists an advantage that a polyglycolic acid layer can be crystallized in a short heating time.
  • An object of the present invention is to provide a method capable of stably producing a multi-layer stretch-molded product that hardly causes delamination due to impact.
  • the present inventors compared a laminate comprising a layer containing an amorphous polyglycolic acid resin and a layer containing another thermoplastic resin adjacent thereto. It is possible to crystallize a polyglycolic acid resin even when heated (aging) at a low temperature, and can reliably prevent deformation during stretch molding. It has been found that a multilayer stretched molded article having excellent delamination resistance due to impact can be obtained by heating the laminate so that the density of the resin-containing layer becomes a predetermined density, and the present invention has been completed. It was.
  • the method for producing a multilayer stretched molded article of the present invention uses an amorphous polyglycolic acid resin so that the density of the layer containing the crystallized polyglycolic acid resin is 1.540 g / cm 3 or more.
  • the thickness of the layer containing the amorphous polyglycolic acid resin is preferably 1 to 500 ⁇ m, and the thickness of the laminate is preferably 3.6 mm or less.
  • the other thermoplastic resins include polyester resins, polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyurethane resins, ethylene / vinyl alcohol resins, ) At least one thermoplastic resin selected from the group consisting of acrylic acid resins, nylon resins, sulfide resins and polycarbonate resins is preferred.
  • the outermost layer of the laminate is selected from the group consisting of a polyester resin, a polystyrene resin, a polyvinyl chloride resin, a (meth) acrylic acid resin, a sulfide resin, and a polycarbonate resin. This is particularly useful when the layer contains at least one thermoplastic resin.
  • amorphous means a state in which 95% or more of the observation field is amorphous in the crystal state observation using a polarizing microscope.
  • crystal growth means a state in which 95% or more of the observation field is filled with spherulites in a crystal state observation using a polarizing microscope.
  • the method for producing a multilayer stretched molded product of the present invention includes: Lamination comprising a layer containing an amorphous polyglycolic acid resin and a layer containing another thermoplastic resin adjacent thereto so that the density of the layer containing the crystallized polyglycolic acid resin becomes a predetermined density
  • PGA resin polyglycolic acid resin
  • formula (1) A glycolic acid homopolymer consisting only of glycolic acid repeating units represented by the formula (hereinafter referred to as “PGA homopolymer”, including a ring-opened polymer of glycolide which is a bimolecular cyclic ester of glycolic acid).
  • PGA copolymer a polyglycolic acid copolymer containing glycolic acid repeating units (hereinafter referred to as “PGA copolymer”).
  • Such PGA-type resin may be used individually by 1 type, or may use 2 or more types together.
  • the PGA homopolymer can be synthesized by dehydration polycondensation of glycolic acid, dealcohol polycondensation of glycolic acid alkyl ester, ring-opening polymerization of glycolide, or the like. Further, a PGA copolymer can be synthesized by using a comonomer in combination in these polycondensation reaction and ring-opening polymerization reaction.
  • Examples of the comonomer include ethylene oxalate (that is, 1,4-dioxane-2,3-dione), lactides, and lactones (for example, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.), carbonates (eg, trimethylene carbonate), ethers (eg, 1,3-dioxane), ether esters (eg, Cyclic monomers such as dioxanone) and amides (such as ⁇ -caprolactam); hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6-hydroxycaproic acid, or alkyls thereof Ester; ethylene glycol, 1, 4 It may be mentioned an aliphatic diol
  • Examples of the catalyst used in the polycondensation reaction and ring-opening polymerization reaction include tin compounds such as tin halides and tin organic carboxylates; titanium compounds such as alkoxy titanates; aluminum compounds such as alkoxy aluminums; zirconium acetylacetone and the like And known catalysts such as antimony compounds such as antimony halides and antimony oxides.
  • the PGA-based resin can be produced by a known polymerization method such as melt polymerization, solid phase polymerization, or a combination thereof.
  • the polymerization temperature is preferably 120 to 300 ° C., more preferably 130 to 250 ° C. 140 to 240 ° C is particularly preferable, and 150 to 230 ° C is most preferable.
  • the polymerization temperature is less than the lower limit, the polymerization tends not to proceed sufficiently.
  • the polymerization temperature exceeds the upper limit, the produced resin tends to be thermally decomposed.
  • the polymerization time of the PGA resin is preferably 2 minutes to 50 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours.
  • the polymerization time is less than the lower limit, the polymerization does not proceed sufficiently, whereas when the upper limit is exceeded, the generated resin tends to be colored.
  • the content of the glycolic acid repeating unit represented by the formula (1) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. 100 mass% is particularly preferable. If the content of the glycolic acid repeating unit is less than the lower limit, the crystallinity of the PGA resin is lowered, and the gas barrier property of the layer containing the PGA resin tends to be lowered.
  • the weight average molecular weight of the PGA resin is preferably 30,000 to 800,000, more preferably 50,000 to 500,000. If the weight average molecular weight of the PGA-based resin is less than the lower limit, the mechanical strength of the layer containing the PGA-based resin tends to decrease, whereas if it exceeds the upper limit, melt extrusion and injection molding tend to be difficult.
  • the weight average molecular weight is a polymethylmethacrylate conversion value measured by gel permeation chromatography (GPC).
  • the melt viscosity (temperature: 270 ° C., shear rate: 122 sec ⁇ 1 ) of the PGA resin is preferably 50 to 3000 Pa ⁇ s, more preferably 100 to 2000 Pa ⁇ s, and particularly preferably 100 to 1000 Pa ⁇ s. . If the melt viscosity is less than the lower limit, the mechanical strength of the layer containing the PGA-based resin tends to decrease, whereas if it exceeds the upper limit, melt extrusion and injection molding tend to be difficult.
  • the PGA resin according to the present invention can be used as it is for the layer containing the amorphous PGA resin in the laminate used in the present invention. It is preferable to mix and use as a polyglycolic acid resin composition (hereinafter referred to as “PGA resin composition”). Mixing with a thermal stabilizer improves thermal stability, and mixing with a terminal blocker improves water resistance. Moreover, an inorganic filler, a plasticizer, another thermoplastic resin, etc. may be added to the PGA resin or the PGA resin composition as necessary, and further, a light stabilizer, a moistureproof agent, a waterproofing agent. Various additives such as an agent, a water repellent, a lubricant, a release agent, a coupling agent, a pigment, and a dye may be added.
  • heat stabilizer examples include cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-tert-butyl).
  • Phosphates having a pentaerythritol skeleton such as phenyl) phosphite and cyclic neopentanetetraylbis (octadecyl) phosphite; alkyl groups such as mono- or di-stearyl acid phosphate or mixtures thereof (preferably having a carbon number) 8-24) alkyl phosphates or phosphite alkyl esters; metal carbonates such as calcium carbonate and strontium carbonate; bis [2- (2-hydroxybenzoyl) hydrazine] dodecanoic acid, N, N′-bis [ 3- (3,5-Di- Hydrazine compounds having a —CONHNH—CO— unit such as —butyl-4-hydroxyphenyl) propionyl] hydrazine; Triazole compounds such as 3- (N-salicyloyl) amino-1,2,4-triazole; Triazine compounds Etc.
  • the amount of such a heat stabilizer added is preferably 0.001 to 3 parts by mass, more preferably 0.003 to 1 part by mass, and 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the PGA resin. Part is particularly preferred.
  • the mixing method of the PGA resin and the heat stabilizer is not particularly limited, and a known method such as dry blending or melt kneading can be applied. However, melt kneading is preferable because uniform mixing is possible.
  • a thermal stabilizer is added to the PGA resin at the supply port of the extruder from the viewpoint of reducing mixing unevenness and improving the thermal stability of the PGA resin composition. Is preferred.
  • end capping agent examples include carbodiimide compounds including monocarbodiimide and polycarbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide; 2,2′-m-phenylenebis (2-oxazoline), 2 , 2'-p-phenylenebis (2-oxazoline), 2-phenyl-2-oxazoline, styrene-isopropenyl-2-oxazoline and the like; 2-methoxy-5,6-dihydro-4H-1,3 -Oxazine compounds such as oxazine; epoxy compounds such as N-glycidyl phthalimide, cyclohexene oxide, and triglycidyl isocyanurate. These end capping agents may be used alone or in combination of two or more.
  • the amount of such an end-capping agent added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, and 0.2 to 1 part by mass with respect to 100 parts by mass of the PGA resin. Is particularly preferred.
  • the mixing method of the PGA-based resin and the end-capping agent is not particularly limited, and a known method such as dry blending or melt kneading can be applied, but melt kneading is preferable from the viewpoint of uniform mixing.
  • the thermal stabilizer and the end-capping agent may be simultaneously added to the PGA-based resin.
  • melt-knead preferably melt knead
  • the heat stabilizer is added to the PGA-based resin at the supply port of the extruder and melt-kneaded in a cylinder.
  • a terminal sealing agent is added to the middle of the cylinder using a side feeder or the like and melt knead. This tends to further improve the thermal stability and water resistance of the PGA resin composition.
  • the drying temperature is preferably 120 to 225 ° C, more preferably 150 to 220 ° C.
  • the drying time is preferably 0.5 to 95 hours, and more preferably 1 to 48 hours.
  • the laminate used in the present invention comprises a layer containing an amorphous PGA resin (hereinafter referred to as “amorphous PGA resin layer”) and a layer containing another thermoplastic resin adjacent thereto (hereinafter referred to as “heat”).
  • a plastic resin layer As a method for producing such a laminate, for example, as described in JP-A No. 2003-20344, a PGA resin composition (or PGA resin) and other thermoplastic resins (or compositions thereof) ) In the form of a film and affixing them; PGA-based resin composition (or PGA-based resin) is formed into a film and this is formed from another thermoplastic resin (or its composition).
  • the coextrusion method and the co-injection method have an advantage that the molding process is simple.
  • thermoplastic resin examples include polyester resins such as polyethylene terephthalate and polylactic acid, polyolefin resins such as polyethylene, polypropylene, and ethylene / propylene copolymers, polystyrene resins such as polystyrene and styrene / butadiene copolymers, and polyvinyl chloride resins. Polyvinylidene chloride resin, polyurethane resin, ethylene / vinyl alcohol resin, (meth) acrylic acid resin, nylon resin, sulfide resin, polycarbonate resin and the like. These thermoplastic resins may be used alone or in combination of two or more.
  • a polyester-based resin is more preferable, and at least one of the diol component and the dicarboxylic acid component is an aromatic compound.
  • Aromatic polyester resins are particularly preferred, and aromatic polyester resins obtained from aromatic dicarboxylic acids are most preferred.
  • the thickness of the laminate is preferably 3.6 mm or less, more preferably 3.4 mm or less, and particularly preferably 3.2 mm or less. If the thickness of the laminate exceeds the upper limit, an amorphous PGA-based resin layer is difficult to obtain, and delamination due to impact tends to occur in the multilayer stretched molded product.
  • the amorphous PGA resin film or the amorphous PGA resin may be used as the molding temperature (set value) of the film containing the amorphous PGA resin or the amorphous PGA resin layer.
  • the lower limit is preferably a melting point Tm + 18 ° C. or higher, more preferably a melting point Tm + 23 ° C. or higher, and particularly preferably a melting point Tm + 28 ° C. or higher.
  • molding temperature is set below the lower limit, it is difficult to obtain an amorphous PGA-based resin film or an amorphous PGA-based resin layer, and delamination due to impact tends to occur in the multilayer stretched molded product.
  • molding temperature setting value
  • 300 degrees C or less is preferable, 290 degrees C or less is more preferable, and 280 degrees C or less is especially preferable.
  • the molding temperature of the thermoplastic resin film or the thermoplastic resin layer is appropriately set according to the physical properties of the thermoplastic resin to be used.
  • the molding temperature of the PET film or PET layer is preferably 280 to 310 ° C, more preferably 285 to 305 ° C.
  • the molding temperature of the PET film or the PET layer is less than the lower limit, an unmelted product is generated, and it tends to be difficult to obtain a target laminate. There is a tendency that molding becomes difficult due to conversion.
  • the thickness of the amorphous PGA resin layer is preferably 1 to 500 ⁇ m, more preferably 1 to 300 ⁇ m, and particularly preferably 1 to 200 ⁇ m. If the thickness of the amorphous PGA-based resin layer is less than the lower limit, the gas barrier property of the multilayer stretched molded product tends to decrease. On the other hand, if the thickness exceeds the upper limit, the PGA-based resin layer has a sufficient density in the crystallization step. However, delamination due to impact tends to occur in the multilayer stretched molded product.
  • the composition ratio of the amorphous PGA-based resin layer with respect to the entire laminate is preferably 1 to 10%, more preferably 1 to 5% on a mass basis.
  • the composition ratio of the amorphous PGA-based resin layer is less than the lower limit, the gas barrier property of the multilayer stretched molded product tends to be lowered.
  • the upper limit is exceeded, a large amount of stress is required at the time of stretch molding and multilayer stretching. The transparency of the molded product tends to decrease.
  • the method for producing a multilayer stretched molded product of the present invention comprises heating a laminate comprising the above amorphous PGA resin layer and a thermoplastic resin layer adjacent thereto to crystallize the amorphous PGA resin layer. It is a method including a step of crystallizing (crystallization step) and a step of stretching and molding the laminate obtained thereby (stretching step).
  • the laminate including the amorphous PGA resin layer is heated so that the density of the crystallized PGA resin layer is 1.540 g / cm 3 or more.
  • the density of the crystallized PGA resin layer is less than the lower limit, crystallization is insufficient, and delamination due to impact occurs in the multilayer stretched molded product.
  • the crystallization of the amorphous PGA resin layer can be confirmed by observing the crystallization state using a polarizing microscope. That is, if the density of the crystallized PGA-based resin layer is 1.540 g / cm 3 or more, 95% or more of spherulites are present.
  • the density of the crystallized PGA resin layer is preferably 1.545 g / cm 3 or more. 1.550 g / cm 3 or more is more preferable.
  • the upper limit of the density of the crystallized PGA resin layer is preferably 1.580 g / cm 3 or less.
  • the laminate including the amorphous PGA resin layer is heated at 50 ° C. or higher and lower than 70 ° C.
  • the laminate including the amorphous PGA resin layer is heated at 50 ° C. or higher and lower than 70 ° C.
  • the laminate including the amorphous PGA resin layer is heated at 50 ° C. or higher and lower than 70 ° C.
  • deformation during stretch molding hardly occurs, and multi-layer stretching excellent in delamination resistance and transparency due to impact. It becomes possible to produce a molded product with high yield.
  • the heating temperature is less than the lower limit
  • crystallization and densification of the crystallized PGA-based resin layer proceed sufficiently when heated at a temperature exceeding the upper limit for a long time. It becomes difficult to obtain a multilayer stretch molded product stably because the laminate including the resin layer is easily deformed.
  • the heating temperature is preferably set to 55 ° C. or higher and 65 ° C. or lower.
  • thermoplastic resin having a low glass transition temperature for example, polyester resin, polystyrene resin, polyvinyl chloride resin, (meth) acrylic.
  • the present invention is particularly useful when producing a multilayer stretched molded article having an outermost layer containing an acid resin, sulfide resin, or polycarbonate resin.
  • the heating time in the crystallization process according to the present invention is such that the shape of the laminate, the thickness of the amorphous PGA resin layer, and the heating temperature are used so that the crystallized PGA resin layer having the above density can be obtained with certainty.
  • the heating time is set to 1 to 10 hours.
  • a laminated body having an amorphous PGA resin layer thickness of 300 to 500 ⁇ m is heated at 50 ° C.
  • the heating time is set to 2 to 48 hours (preferably 3 to 30 hours). . If the heating time is less than the lower limit, the amorphous PGA resin layer may not be sufficiently crystallized, and a crystallized PGA resin layer having the density may not be obtained. On the other hand, if the upper limit is exceeded, crystallization may proceed excessively, and stretch molding may be difficult.
  • the laminate is heated at the heating temperature and heating time described above, it is possible to use a known heating device such as a hot air dryer, an infrared heater, an electromagnetic heater, or a heating medium heater. it can.
  • a known heating device such as a hot air dryer, an infrared heater, an electromagnetic heater, or a heating medium heater. it can.
  • the stretching step according to the present invention is a step of stretch-molding the laminate obtained in the crystallization step, that is, a laminate comprising the crystallized PGA resin layer.
  • production of the delamination by the impact between a crystallized PGA type-resin layer and a thermoplastic resin layer is suppressed, and the multilayer stretched molding excellent in gas barrier property and transparency can be obtained.
  • the density of the PGA resin layer is increased by performing heat treatment at a relatively low temperature on the laminate including the amorphous PGA resin layer in advance. In this stretching step, the laminate is hardly deformed, and a multilayer stretched molded product having a predetermined shape and dimensions can be obtained stably.
  • the stretch molding method is not particularly limited, and known stretching methods described in JP-A No. 2003-20344, JP-A No. 2003-136657, JP-T No. 2005-526642, International Publication No. 2006/107099, and the like.
  • a molding method, a stretch blow molding method, or the like can be employed.
  • the shape of the multilayer stretched molded product thus obtained is not particularly limited, and examples thereof include a film shape, a sheet shape, and a hollow shape.
  • a multilayer stretched film, a multilayer stretched sheet, and a multilayer stretched hollow Examples include containers.
  • ⁇ Polymerization reaction rate> A certain amount of PGA resin was added to dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) in which 4-chlorobenzophenone (manufactured by Kanto Chemical Co., Ltd.) was dissolved at a constant concentration as an internal standard substance. The precipitate was filtered. The filtrate was analyzed using gas chromatography (“GC-2010” manufactured by Shimadzu Corporation) under the following conditions, the glycolide content in the PGA resin was determined, and the polymerization reaction rate was calculated.
  • GC-2010 gas chromatography
  • the sample solution was injected into the GPC apparatus within 30 minutes after the amorphous sheet was dissolved.
  • PGA resin layer The inner and outer layers of the preform were peeled off, and an intermediate layer (PGA resin layer) was collected.
  • Six-stage density gradient tubes were prepared using dichloromethane and carbon tetrachloride in a density range of 1.48 to 1.58 g / cm 3 , and the density of the PGA resin layer was measured using these.
  • ⁇ Crystallization temperature Tc1 and calorific value ⁇ Hc1> The inner and outer layers of the preform are peeled to collect an intermediate layer (PGA resin layer), and a differential scanning calorimeter (“DSC30 / TC15” manufactured by METTLER TOLEDO) is used, and the temperature is 0 ° C. to 20 ° C. under nitrogen flow. The temperature was raised at / min. The maximum temperature of the exothermic peak corresponding to crystallization at the time of temperature rise was defined as the crystallization temperature Tc1 of the PGA resin layer. Further, the heat generation amount ⁇ Hc1 at the time of crystallization was determined from this heat generation peak.
  • ⁇ Crystallization temperature Tc2> The sufficiently dried PGA resin composition was melt-pressed with a heat press at 280 ° C. to prepare a 200 ⁇ m sheet. A predetermined amount is cut out from this sheet and heated to 280 ° C. while increasing the temperature from ⁇ 50 ° C. to 20 ° C./min under a nitrogen flow using a differential scanning calorimeter (“DSC30 / TC15” manufactured by METTLER TOLEDO). did. Then, it cooled to room temperature at 20 degree-C / min. The maximum temperature of the exothermic peak due to crystallization during cooling was defined as the crystallization temperature Tc2 of the PGA resin composition.
  • ⁇ Surface roughness Ra> The inner and outer layers of the bottle were peeled off, and an intermediate layer (PGA resin layer) was collected.
  • the surface roughness of the PGA resin layer (the roughness of the interface with the outer PET layer) was measured using a stylus type surface roughness meter ("Surfcom 550AD" manufactured by Tokyo Seimitsu Co., Ltd.). It was measured.
  • the measurement conditions were a stylus cone type 5 ⁇ mR, a measurement force of 4 mN or less, and a cutoff of 0.08 mm.
  • the place was arbitrarily changed and the said measurement was implemented 10 times, and the arithmetic mean value of the obtained result was made into arithmetic mean surface roughness Ra.
  • ⁇ Delamination resistance> The bottle was filled with 4.2 atmospheres of carbonated water, the stopper was closed, and the bottle was allowed to stand at 23 ° C. for 24 hours. Then, a pendulum impact test was performed, and delamination between the outer PET layer and the intermediate layer (PGA resin layer) was observed. The presence or absence was observed. This impact test was performed on 20 bottles, and the number of bottles in which delamination did not occur was measured.
  • the PGA resin and PGA resin composition used in Examples and Comparative Examples were prepared by the following method.
  • a catalyst was prepared such that high-purity glycolide (manufactured by Kureha Co., Ltd.) as a raw material monomer and 1-dodecanol as an initiator was 0.2 mol% based on glycolide.
  • tin dichloride was charged into a reactor so as to be 30 ppm with respect to glycolide, and continuously polymerized with an average residence time of 20 minutes while being controlled at 200 to 210 ° C. The obtained polymer was taken out in the form of particles, and this was further subjected to solid phase polymerization at 170 ° C.
  • the powdery PGA resin was obtained.
  • a PGA resin composition was prepared using a twin-screw kneading extruder (“TEM41SS” manufactured by Toshiba Machine Co., Ltd.). This twin-screw kneader-extruder is equipped with an electric heater that can individually control the temperature in 13 regions. This temperature was controlled so that the maximum temperature of the cylinder of the extruder was 275 ° C.
  • TEM41SS twin-screw kneading extruder
  • the powdery PGA resin was continuously supplied to the biaxial kneading extruder.
  • the thermal stabilizer (“ADK STAB AX-71” manufactured by Asahi Denka Kogyo Co., Ltd.) was added at a ratio of 0.020 parts by mass with respect to 100 parts by mass of PGA resin, and N, N-2, 6-Diisopropylphenylcarbodiimide (“DIPC” manufactured by Kawaguchi Chemical Industry Co., Ltd.) was continuously supplied in a molten state at a ratio of 0.3 part by mass with respect to 100 parts by mass of the PGA resin, and melt-kneaded.
  • DIPC 6-Diisopropylphenylcarbodiimide
  • the strand discharged from the die of the extruder was cooled and cut using a pelletizer to obtain a pellet-like PGA resin composition.
  • the obtained pellet was heat-treated at 170 ° C. for 17 hours.
  • the glycolide content of the PGA resin composition was 0.1% by mass or less, and the crystallization temperature Tc2 was 134 ° C.
  • Example 1 ⁇ Co-injection molding>
  • the PGA resin composition prepared as described above was used as the intermediate layer resin, and the inner and outer layer resins were polyethylene terephthalate (“CB602S” manufactured by Totobo Co., Ltd., weight average molecular weight: 20,000, melt viscosity (temperature: 290 ° C., Using a co-injection molding machine having a shear rate of 122 sec ⁇ 1 ): 550 Pa ⁇ s, a glass transition temperature: 75 ° C., and a melting point: 249 ° C.
  • CB602S polyethylene terephthalate
  • a colorless and transparent bottle preform (preform thickness: 3.15 mm, PGA resin layer thickness: 200 ⁇ m) composed of three layers of PGA / PET (PGA filling amount: 3 mass%). Reform ”).
  • the temperature of the intermediate layer barrel and the runner was set to 255 ° C, and the temperature of the inner and outer layer barrels and the runner was set to 290 ° C.
  • the crystallization state of the intermediate layer (PGA resin layer) of the obtained three-layer preform was observed using a polarizing microscope (“BH-2” manufactured by Olympus Corporation), no crystals were formed in the entire observation field. It was confirmed that they did not.
  • the three-layer preform subjected to the aging treatment as described above was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • Example 2 A three-layer preform produced in the same manner as in Example 1 was heated in a hot air dryer set at 65 ° C. for 1 hour.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform after the heat treatment, the crystallization temperature Tc1, and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods. The results are shown in Table 1.
  • the three-layer preform subjected to the aging treatment as described above is stretch blow molded in the same manner as in Example 1 and is a colorless and transparent bottle comprising three layers of PET / PGA / PET (PGA filling amount: 3 mass%).
  • PGA filling amount 3 mass%.
  • the yield, arithmetic average surface roughness (roughness of the interface with the outer PET layer) Ra, and delamination resistance were measured according to the above methods. The results are shown in Table 1.
  • the three-layer preform subjected to the aging treatment as described above was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • the three-layer preform not subjected to the aging treatment was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density, the crystallization temperature Tc1, and the calorific value ⁇ Hc1 at the time of crystallization were measured according to the above methods. The results are shown in Table 1.
  • Example 2 (Comparative Example 2) ⁇ Aging> A three-layer preform produced in the same manner as in Example 1 was heated in a hot air dryer set at 70 ° C. for 0.5 hour. The density of the intermediate layer (PGA resin layer) of the three-layer preform after the heat treatment was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • the three-layer preform subjected to the aging treatment as described above is stretch blow molded in the same manner as in Example 1 and is a colorless and transparent bottle comprising three layers of PET / PGA / PET (PGA filling amount: 3 mass%).
  • PGA filling amount 3 mass%.
  • the yield and arithmetic average surface roughness (roughness of the interface with the outer PET layer) Ra were measured according to the methods described above. The results are shown in Table 1.
  • the three-layer preform subjected to the aging treatment as described above was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • Example 3 (Comparative Example 3) ⁇ Aging> A three-layer preform produced in the same manner as in Example 1 was heated in a hot air dryer set at 75 ° C. for 0.5 hour. The density of the intermediate layer (PGA resin layer) of the three-layer preform after the heat treatment was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • the three-layer preform subjected to the aging treatment as described above is stretch blow molded in the same manner as in Example 1 and is a colorless and transparent bottle comprising three layers of PET / PGA / PET (PGA filling amount: 3 mass%).
  • PGA filling amount 3 mass%.
  • the yield and arithmetic average surface roughness (roughness of the interface with the outer PET layer) Ra were measured according to the methods described above. The results are shown in Table 1.
  • the three-layer preform subjected to the aging treatment as described above was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • Example 4 ⁇ Co-injection molding> Example 1 except that the temperature of the intermediate layer barrel and runner was changed to 245 ° C., and the injection amount of the resin was adjusted so that the preform thickness was 4.10 nm and the PGA resin layer thickness was 260 ⁇ m.
  • a colorless and transparent bottle preform (hereinafter referred to as “three-layer preform”) composed of three layers of PET / PGA / PET (PGA filling amount: 3 mass%) was produced.
  • the three-layer preform not subjected to the aging treatment was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • the three-layer preform not subjected to the aging treatment was separately preheated to 110 ° C. using the stretch blow molding machine and then rapidly cooled.
  • the density of the intermediate layer (PGA resin layer) of the three-layer preform was measured according to the above method. The results are shown in Table 1. Further, when the crystallization temperature Tc1 of the PGA resin layer and the calorific value ⁇ Hc1 during crystallization were measured according to the above methods, no exothermic peak was detected.
  • the amorphous PGA resin layer was subjected to aging treatment at a predetermined temperature to obtain crystals having a predetermined density.
  • a crystallized PGA resin layer it is equipped with a crystallized PGA resin layer with a smooth interface with the outer PET layer without deformation of the three-layer preform during stretch blow molding, and is resistant to delamination and transparency due to impact It was confirmed that a multilayer stretched molded product (bottle) having excellent properties can be obtained in a high yield.
  • Example 1 since the exothermic peak by crystallization was not detected in the PGA resin layer after the aging treatment, it was confirmed that the PGA resin layer was completely crystallized by the aging treatment.
  • Example 2 crystallization of the PGA resin layer occurred, but an exothermic peak due to crystallization was detected in the PGA resin layer after the aging treatment, and the amorphous PGA resin remained.
  • the density of the PGA resin layer after the aging treatment is 1.545 g / cm 3 or more, the remaining amorphous PGA resin can be crystallized by preheating at the time of stretch blow molding, and at the time of stretch blow molding ( After preheating), it was confirmed that the PGA resin layer was completely crystallized.
  • the amorphous PGA resin layer is subjected to an aging treatment at 70 ° C. or higher (Comparative Examples 2 to 3), the three-layer process is performed so that the density of the PGA resin layer is 1.540 g / cm 3 or higher. It was found that even if the aging treatment was applied to the reform, a bottle having a desired shape and size could not be stably obtained in the subsequent stretch blow molding, and the yield of the target bottle was lowered.
  • the density of the crystallized PGA resin layer is 1.540 g / cm 3. Even if it is 3 or more, since the amorphous material is not crystallized, the smoothness of the surface in contact with the outer PET layer of the PGA resin layer is low, and impact is caused between the PGA resin layer and the outer PET layer. Due to delamination. The reason is presumed as follows. That is, the PGA resin layer crystallized in the preform molding process has a non-uniform crystal state, and when a three-layer preform provided with such a PGA resin layer is stretched, the interface with the outer PET layer becomes rough. Therefore, it is presumed that delamination due to impact occurred.
  • the method for producing a multilayer stretched molded product of the present invention is a method capable of producing a multilayer stretched molded product with a high yield, and is useful as a method suitable for mass production of the multilayer stretched molded product.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un article étiré-moulé, multicouche, qui comporte une étape de cristallisation, suivant laquelle un corps stratifié pourvu d'une couche contenant une résine à base d'un poly(acide glycolique) amorphe et d'une couche adjacente contenant une autre résine thermoplastique est chauffé à une température entre 50°C et 70°C pour former une couche contenant une résine à base d'un poly(acide glycolique) cristallisé, de façon que la couche contenant la résine à base d'un poly(acide glycolique) cristallisé présente une masse volumique d'au moins 1,540 g/cm3, et une étape d'étirage pour l'étirage-moulage du corps stratifié pourvu de la couche contenant la résine à base d'un poly(acide glycolique) cristallisé.
PCT/JP2011/052034 2010-02-04 2011-02-01 Procédé de fabrication d'un article étiré-moulé multicouche WO2011096395A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN118386581A (zh) * 2024-06-28 2024-07-26 广东树业环保材料有限公司 一种高透光率双向拉伸聚乳酸膜及其制备方法和应用
JP7528748B2 (ja) 2020-11-30 2024-08-06 三菱瓦斯化学株式会社 多層容器

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WO2005072944A1 (fr) * 2004-01-30 2005-08-11 Kureha Corporation Conteneur creux et proc)d) de production de celui-ci
WO2007088833A1 (fr) * 2006-01-31 2007-08-09 Yoshimura Kasei Co., Ltd. Procede de thermoformage de feuilles stratifiees biodegradables
WO2009107425A1 (fr) * 2008-02-28 2009-09-03 株式会社クレハ Film en acide polyglycolique étiré biaxialement de manière successive, son procédé de production et film multicouche
WO2009154150A1 (fr) * 2008-06-16 2009-12-23 東レ株式会社 Film de dépôt en phase vapeur

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JP4861019B2 (ja) * 2006-01-31 2012-01-25 独立行政法人科学技術振興機構 ヒトＴＮＦ−αに対する抗体酵素およびその利用

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WO2005072944A1 (fr) * 2004-01-30 2005-08-11 Kureha Corporation Conteneur creux et proc)d) de production de celui-ci
WO2007088833A1 (fr) * 2006-01-31 2007-08-09 Yoshimura Kasei Co., Ltd. Procede de thermoformage de feuilles stratifiees biodegradables
WO2009107425A1 (fr) * 2008-02-28 2009-09-03 株式会社クレハ Film en acide polyglycolique étiré biaxialement de manière successive, son procédé de production et film multicouche
WO2009154150A1 (fr) * 2008-06-16 2009-12-23 東レ株式会社 Film de dépôt en phase vapeur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7528748B2 (ja) 2020-11-30 2024-08-06 三菱瓦斯化学株式会社 多層容器
CN118386581A (zh) * 2024-06-28 2024-07-26 广东树业环保材料有限公司 一种高透光率双向拉伸聚乳酸膜及其制备方法和应用

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