WO2004003077A1 - Receptacle produit par formage par etirage - Google Patents

Receptacle produit par formage par etirage Download PDF

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Publication number
WO2004003077A1
WO2004003077A1 PCT/JP2002/006624 JP0206624W WO2004003077A1 WO 2004003077 A1 WO2004003077 A1 WO 2004003077A1 JP 0206624 W JP0206624 W JP 0206624W WO 2004003077 A1 WO2004003077 A1 WO 2004003077A1
Authority
WO
WIPO (PCT)
Prior art keywords
polylactic acid
stretch
resin
container
optically active
Prior art date
Application number
PCT/JP2002/006624
Other languages
English (en)
Japanese (ja)
Inventor
Takurou Itoh
Hiroto Watanabe
Original Assignee
Toyo Seikan Kaisha,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 Toyo Seikan Kaisha,Ltd. filed Critical Toyo Seikan Kaisha,Ltd.
Priority to AU2002313314A priority Critical patent/AU2002313314A1/en
Priority to PCT/JP2002/006624 priority patent/WO2004003077A1/fr
Publication of WO2004003077A1 publication Critical patent/WO2004003077A1/fr

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Classifications

    • 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
    • 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
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a stretch-formed container formed from a resin mainly composed of polylactic acid, and more particularly, to a stretch-formed container having excellent stretch-moldability and improved heat resistance and transparency of the container.
  • the present invention relates to a stretch-formed container formed from a resin mainly composed of polylactic acid.
  • biodegradable plastic is excellent in harmony with the environment such as biodegradability, but it has good moldability and mechanical strength of stretch-formed products. However, they could not be satisfied with such points.
  • aliphatic polyesters have poor melt properties of resin, and can be used for direct blow molding, injection stretch molding, and sheet thermoforming. There is a problem that it is difficult to form such as a foam. For this reason, the melt tension is improved by adding an inorganic filler (Japanese Patent Application Laid-Open No. Hei 5-289263). Higher molecular weight by chain stretching using acid anhydride (Japanese Patent Application Laid-Open No. Hei 7-250278) has been proposed.
  • aliphatic polyesters include, for example, P-hydroxybutyrate (PHB), and 3-hydroxybutyrate (3HB). And 3 — Hydroxylate Rate (3 HV) with random copolymers, poly ( ⁇ — force pro- lectone) (PCL), polybutylene Known are xinate (PBS), polybutylene succinate (ADBA), polylactic acid (LLA) and the like.
  • Lactic acid is listed.
  • Polylactic acid (PL-A) is a resin made from cereal starch such as corn. Fermented starch, fermented lactic acid, and lactic acid are treated as monomers. It is a polymer. It is generally produced by a ring-opening polymerization method of lactide, which is a dimer, and a direct polycondensation method. This polymer is decomposed by water and carbon dioxide by natural microbes, and it is expected to become a complete recycling system type resin. It has been done.
  • the glass transition point (T g) has an advantage that the glass transition point (T g) is about 60 ° C., which is close to the T g of polyethylene terephthalate. .
  • polylactic acid which is generally used in the field of packaging containers, like other aliphatic polyesters, still has to be solved in terms of moldability and the like.
  • polylactic acid includes D-lactic acid, L-lactic acid, and DL-lactic acid, and among them, polylactic acid composed of monolactic acid is also used.
  • L-lactic acid can be used in the field of packaging containers because it forms oriented crystals by stretching and improves mechanical strength such as yield point strength, elastic modulus, and thermal dimensional stability.
  • polylactic acid which consists solely of L-lactic acid, has high optical purity and high crystallinity, and forms crystals upon heating the preform and subsequent stretching. And overstretching cause whitening, making it difficult to combine orientational crystallinity and transparency, which poses a practical problem. Disclosure of the invention
  • an object of the present invention is to provide a stretch container having transparency, stretch moldability, and thermal dimensional stability in a stretch-molded container formed of a resin mainly composed of polylactic acid. 0% to provide a molded container.
  • the crystallization start temperature is 75 ° C or more, and the temperature measured by a differential scanning calorimeter is 7 ° C.
  • a stretch-formed container characterized by having substantially two peaks in a crystallization exothermic temperature range of 5 to 160 ° C. is provided.
  • Polylactic acid has a higher ratio of optically active isomer (d) and a lower ratio of optically active isomer (d) Is a pre-
  • the axial shrinkage of the side wall at a temperature of 55 ° C is 4% or less
  • the light transmittance at a wavelength of 465 nm on the side wall is 60% or more.
  • FIG. 1 is a diagram showing a general polylactic acid DSC curve.
  • FIG. 2 is a view showing the DSC curve of polylactic acid used in Example 1.
  • FIG. 3 is a view showing a DSC curve of polylactic acid used in Comparative Examples 1 and 2.
  • BEST MODE FOR CARRYING OUT THE INVENTION The stretch-formed container of the present invention has a crystallization onset temperature of 75 ° C. or higher and a temperature of 75 to 160 ° C. measured by a differential scanning calorimeter (DSC). Some are characterized by having substantially two peaks in the crystallization exothermic temperature range of ° C.
  • Polylactic acid has the following formula (1) Chemical 1
  • L-lactic acid composed of repeating units represented by one (1), composed of only L-lactic acid, and D-lactic acid only Poly (D-lactic acid), and poly (DL-lactic acid) in which L-lactic acid unit and D-lactic acid unit are present at an arbitrary ratio.
  • polylactic acid As mentioned above, it is desirable to use polylactic acid with high optical purity in order to improve the mechanical strength of the container.However, because of its high crystallinity, stretch molding is preferred. It is easy to whiten due to thermal crystallization. On the other hand, optically pure (low optical purity) polylactic acid, which is excellent in stretch moldability, is less likely to be oriented and crystallized in stretch molding, resulting in poor heat resistance.
  • polylactic acid having a crystallization start temperature of 75 ° C. or higher is used to disperse the optically active isomer (d) in the molecular chain unevenly. Thus, it is possible to provide a stretch-molded container having transparency, stretch-moldability, and heat resistance while having biodegradability.
  • the polylactic acid used in the present invention has the composition It is also important that the crystallization onset temperature is 75 ° C or higher, and if the crystallization temperature is lower than 75 ° C, whitening due to excessive elongation occurs during molding. This makes it difficult to stretch.
  • the stretch-formed container of the present invention has substantially two peaks in a crystallization range temperature range of 75 to 160 ° C. measured by a differential scanning calorimeter (DSC). And are important.
  • Figure 1 shows a typical DSC curve of polylactic acid
  • Figure 3 shows a DSC curve of polylactic acid containing 2.0% of the optically active isomer (d). Also has only one peak in the crystallization temperature range.
  • the polylactic acid used in the present invention has two peaks in the crystallization temperature range, as shown in FIG. That is, since the stretch-formed container of the present invention has both a low-temperature crystallization component and a high-temperature crystallization component, stretch-forming can be performed while maintaining transparency. At the same time, it becomes possible to provide an oriented crystal, and at the same time, it is possible to improve the heat resistance. This is also evident from the results of the examples described below.
  • Polylactic acid used in the present invention is, of course, not limited to, but is preferably in the range of 100,000 to 3,000,000, in particular, 2,0000 to 2,500,000. It is preferred to have a weight average molecular weight of The density is 1.26 to 1.20 gcm 3 , the melting point is 1665 to 200 ° C, and the melt flow rate (ASTMD 1238, 190 ° C) is 2 to It is preferably in the range of 20 g Z 10 minutes.
  • polylactic acid (A) having a high ratio of the optically active isomer (d) and polylactic acid having a low ratio of the optically active isomer (d) are used. It is desirable to use (B) by blending it.
  • a high ratio of the optically active isomer (d) means that the optically active isomer (d) is generally contained in the range of 4 to 10%, and the optically active isomer (d) is contained. Is low when the content of the optically active isomer (d) is generally in the range of 0.5 to 1.5%.
  • the optically active isomers in a ratio within the range of 1.5 to 3.5 / 0 .
  • the blending method include a dry blend and a melt blend, and, if necessary, a solid phase polymerization. It is also possible to apply.
  • the above-mentioned polylactic acid can be used alone, or it can be used as a blend with another aliphatic polyester or another resin. It can also be used as Other aliphatic polyesters include 3—hydroxybutyrate, 3—hydroxyvalerate, and 3—hydroxyprolate. , 3-Hydrogen heptanoate, 3-Hydroxy octanoate, 3-Hydroxycinanoate, 3-Hydroxy Polycyanate, r-butyrolactone, ⁇ -valerolactone, ⁇ -force proton, etc. Or one of these copolymers.
  • the container of the present invention can be used as a single layer of the above polylactic acid resin composition or, depending on the properties of the contents, ethylene.
  • layers such as vinyl alcohol copolymer saponified compound, mexylylene adipamide ( ⁇ XD6), cyclic olefin copolymer, etc.
  • ⁇ XD6 mexylylene adipamide
  • cyclic olefin copolymer etc.
  • resins that can be used in the form of a blend or a laminate include a barrier resin, for example, a hydroxyl group that exhibits a barrier property to oxygen.
  • Thermoplastic resin contained, Nylon resin, P / R, Polyester resin, High-trile resin, and exhibits barrier properties to water vapor Cyclic olefin-based copolymers and the like can be mentioned.
  • a hydroxyl group-containing resin is preferred in terms of biodegradability, and any resin can be used as long as thermoforming is possible.
  • This resin has, in its molecular chain, a repeating unit having a hydroxyl group and a unit for imparting thermoformability to the resin.
  • Hydroxyl-containing repeating units are vinyl alcohol units and hydroxyalkyl (meta) acrylate units. Although it does not matter, vinyl alcohol units are preferred in terms of biodegradability.
  • Other units contained in this hydroxyl "a” resin include olefin units such as ethylene and propylene, and vinyl esters such as vinyl acetate. And alkyl (meta) acrylate units, etc. These hydroxyl group-containing resins are at least sufficient to form a film. It must be a molecule.
  • Suitable hydroxyl-containing resins are 10 to 40 mol% of ethylene units, 40 to 88 mol% of vinyl alcohol units, and 50 mol % Or less of the ester-containing vinyl unit.
  • the container of the present invention may contain various coloring agents, fillers, mechanical or organic reinforcing agents, lubricants, plasticizers, leveling agents, surfactants, etc., depending on the intended use. Thickeners, thinners, stabilizers, antioxidants, ultraviolet absorbers, antioxidants and the like can be blended according to known formulations.
  • the stretch blow molded article of the present invention is obtained by biaxially stretching a preform (preform) provided with a layer made of the above-mentioned resin composition of polylactic acid. Manufactured from this.
  • It can be manufactured by extrusion molding, injection molding, or compression molding.
  • the molten resin For example, by extruding the molten resin through a ⁇ die, the thin film of the stretched film, and the compressed air to the film and the cup Molding Sheets for plug-assist molding are molded.
  • the molten resin by extruding the molten resin through a ring die, it is possible to mold a pipe-shaped preform for container molding. .
  • the molten resin is injected into a mold composed of a cavity mold and a core mold by a screw or a plunger.
  • a preform for a three-dimensional container such as a bottle is formed.
  • a three-dimensional preform such as a bottle can be obtained.
  • a technique known per se is used, for example, extrusion molding.
  • a multi-layer preform is manufactured by co-extrusion using a multi-layer die using an extruder corresponding to the resin.
  • a multilayer preform can be formed by a simultaneous co-extrusion method or a sequential co-extrusion method known per se. Furthermore, even in the compression molding method, a multi-layered preform can be produced by forming a multi-layered molten resin by co-extrusion or the like. Wear .
  • the obtained preforms are infrared heating, hot air heating, After being heated by heating means such as frequency induction heating or ultrasonic heating, a stretched molded article is obtained by stretching and blowing in a mold.
  • the stretching temperature varies depending on the type of polylactic acid and the blend or the resin to be laminated, the glass transition point (Tg) of polylactic acid is generally used. ), A temperature of T g + 10 ° C. to T g + 20 ° C. is appropriate.
  • Tg glass transition point
  • the stretching ratio in the machine direction is 1.4 to 4.0 times
  • the stretching ratio in the transverse direction is 1.4 to 4.0 times. Therefore, it is preferable that the stretching is performed so that the area stretching ratio becomes 2 to 16 times.
  • the stretch-molded container of the present invention has an axial shrinkage of the side wall portion at a temperature of 55 ° C of 4% or less, particularly 3% or less. Excellent heat resistance, especially dimensional stability.
  • the stretch-formed container of the present invention is free from whitening due to overstretching or overheating, and has a light transmittance of 60% or more, particularly 70%, at a wavelength of 465 nm on the side wall. % And excellent transparency. Examples Examples of the present invention are shown below. Note that the present invention is not limited to the following embodiments.
  • polylactic acid having a weight-average molecular weight of 160,000 and an optically active isomer (d) ratio of 1.2% (L acty 9100) , 2.0% of a polylactic acid resin (Lacty 900), and 5.0% of a polylactic acid flour (Lacty500).
  • a preform having a diameter of 28 mm0 is injection molded at a mold temperature of 15 ° C under the conditions of 190 ° C to 200 ° C.
  • the preform was reheated to 80 to 90 ° C using an infrared heating heater, and the area stretch ratio was 4 to 10 times using a mold blow molding machine.
  • a bottle having a mean wall thickness of 300 OjUm with a volume of 500 ml was prepared.
  • the point of rising from this baseline was defined as the crystallization onset temperature.
  • the obtained injection molded container was stored in a 55 ° C constant temperature bath for 5 hours, and the dimensional deformation of the container side wall was observed.
  • X was defined as one that shrunk well by 4% in dimension, and one with shrinkage of 4% or less.
  • optically active form (d) 1.2% of polylactic acid tree and 5.0% of optically active isomer (d) of polylactic acid were respectively 78% and 2% by weight.
  • the blend was adjusted to 2%, and a polylactic acid resin composition pellet having an average optically active isomer (d) ratio of 1.% was prepared.
  • the mold temperature was set at 190 ° C to 200 ° C.
  • a preform having a diameter of 28 mm 0 was injection molded at 5 ° C.
  • the obtained preform was reheated to 0 ° C using an infrared heating heater, and the area was stretched at a stretching ratio of 4 to 10 times.
  • optically active compound (d) 1.2 o / o polylactic acid resin and optically active isomer (d): 5.0% % And 22%, and then use a stirring-type vacuum dryer.
  • Polylactic acid resin composition pellets with specific power ⁇ 1. '8% were prepared.
  • a preform having a diameter of 28 mm0 was injection-molded at a mold temperature of 15 ° C under conditions of 190 ° C to 200 ° C. did .
  • a blow molding machine was used at an area stretching ratio of 4 to 10 times. , 500 m
  • a bottle with an average thickness of 3 volume of 3 O O jU m was formed.
  • a polylactic acid tree having a ratio of the optically active isomer (d) of 2.0% was used.
  • a preform with a diameter of 28 mm0 was injection-molded at a mold temperature of 15 ° C under conditions of 190 ° C to 200 ° C. .
  • a blow molding machine was used at an area stretching ratio of 4 to 10 times.
  • a pot with a mean wall thickness of 300 jUm having a volume of 500 ml was formed.
  • Polylactic acid resin having an optically active isomer (d) ratio of 2.0 / 0 was used.
  • a preform having a diameter of 28 mm ⁇ was injection-molded at a mold temperature of 15 ° C under conditions of 190 ° C to 200 ° C.
  • an infrared pressurized thermal heat COMPUTER at the area draw ratio 4 to 1 0 times the draw ratio, use the blanking B over molding machine A 500 ml bottle with an average wall thickness of 300 jUm was molded.
  • Polylactic acid tree containing 1.2% of optically active isomer (d) A polylactic acid resin having a ratio of fat and photoactive isomer (d) of 5.0 / 0 was melt blended to give a weight ratio of 78% and 22%, respectively. , The average optically active isomer (d) ratio power ⁇ 1.
  • An 8% polylactic acid resin composition pellet was prepared.
  • a preform having a diameter of 28 mm0 was formed by injection molding using a mold at a temperature of 190 ° C to 200 ° C and a mold temperature of 15 ° C. .
  • the preform as an infrared heating heater

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention porte sur un réceptacle produit par formage par étirage à partir d'une résine constituée principalement de l'acide polylactique. La résine a une température initiale de cristallisation égale ou supérieure à 75 °C et présente sensiblement deux crêtes lorsqu'on l'observe avec un calorimètre différentiel à balayage dans la plage de températures comprise entre 75 et 160 °C, c'est à ce moment que l'on constate une chaleur de cristallisation. On peut ainsi produire par formage par étirage le réceptacle de l'invention qui présente une grande transparence et une excellente résistance à la chaleur.
PCT/JP2002/006624 2002-06-28 2002-06-28 Receptacle produit par formage par etirage WO2004003077A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002313314A AU2002313314A1 (en) 2002-06-28 2002-06-28 Container formed by stretch forming
PCT/JP2002/006624 WO2004003077A1 (fr) 2002-06-28 2002-06-28 Receptacle produit par formage par etirage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2002/006624 WO2004003077A1 (fr) 2002-06-28 2002-06-28 Receptacle produit par formage par etirage

Publications (1)

Publication Number Publication Date
WO2004003077A1 true WO2004003077A1 (fr) 2004-01-08

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PCT/JP2002/006624 WO2004003077A1 (fr) 2002-06-28 2002-06-28 Receptacle produit par formage par etirage

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AU (1) AU2002313314A1 (fr)
WO (1) WO2004003077A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157408A (ja) * 1995-12-11 1997-06-17 Mitsubishi Plastics Ind Ltd 延伸ポリ乳酸フィルムあるいはシート

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157408A (ja) * 1995-12-11 1997-06-17 Mitsubishi Plastics Ind Ltd 延伸ポリ乳酸フィルムあるいはシート

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AU2002313314A1 (en) 2004-01-19

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