WO2010005043A1 - Film de résine d’acide polylactique - Google Patents

Film de résine d’acide polylactique Download PDF

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Publication number
WO2010005043A1
WO2010005043A1 PCT/JP2009/062495 JP2009062495W WO2010005043A1 WO 2010005043 A1 WO2010005043 A1 WO 2010005043A1 JP 2009062495 W JP2009062495 W JP 2009062495W WO 2010005043 A1 WO2010005043 A1 WO 2010005043A1
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WO
WIPO (PCT)
Prior art keywords
polylactic acid
resin film
acid resin
heat seal
film
Prior art date
Application number
PCT/JP2009/062495
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English (en)
Japanese (ja)
Inventor
太成 松本
一博 田中
克司 渡部
Original Assignee
東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN200980126911.6A priority Critical patent/CN102089364B/zh
Priority to JP2009536946A priority patent/JP5777133B2/ja
Publication of WO2010005043A1 publication Critical patent/WO2010005043A1/fr

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    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • 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

Definitions

  • the present invention relates to a polylactic acid-based resin film excellent in heat sealability, impact resistance, and transparency, particularly excellent for packaging materials, and suitable for the inflation method, which is a relatively inexpensive facility, and excellent in economic efficiency. .
  • plastics produced from general-purpose petroleum-derived raw materials include polyolefins such as polyethylene.
  • polyethylene is usually formed into a bag shape by an inflation method, processed into a bag shape by a process such as heat sealing and cutting with a bag making machine, and then used in a large amount for various packaging films.
  • many attempts have been made to apply polylactic acid to such heat-sealable films.
  • Patent Document 1 a laminated structure consisting of at least two layers of a base material layer and a sealing layer, and heat sealability is imparted based on the difference in melting point or softening point between the base material layer and the sealing layer. Many attempts have been made.
  • Patent Document 2 discloses a film containing a polylactic acid polymer and another aliphatic polyester in a certain ratio.
  • Patent Document 3 discloses a film that defines a unique phase transition index in a product mainly composed of a polylactic acid polymer.
  • Patent Document 4 discloses a film made of a mixture of a polylactic acid resin and a biodegradable polyester other than the polylactic acid resin having a glass transition temperature Tg of 10 ° C. or less.
  • JP-A-8-323946 Japanese Patent Laid-Open No. 11-222528 JP 2003-128797 A JP 2003-292642 A
  • the film described in Patent Document 2 has a problem that transparency is insufficient for packaging materials because of the relatively high content of other aliphatic polyesters.
  • the film described in Patent Document 3 is basically a technique for a stretched film although it is a single film, and has a problem that it is still insufficient in practical terms as a heat sealability.
  • the present invention is excellent in heat sealability, impact resistance and transparency, particularly excellent for packaging materials, and more suitable for the inflation method which is a relatively inexpensive facility. It is intended to provide a polylactic acid-based resin film excellent in the quality.
  • the polylactic acid resin (A) contains 65% by mass or more and 95% by mass or less, melt mass flow rate under 190 ° C. and 2.16 kg load: MFR (g / 10 minutes) is 3 (g / 10 minutes) or more, At least one heat seal layer comprising a composition containing 5% by mass or more and 35% by mass or less of an aliphatic polyester and / or an aliphatic aromatic polyester (B) other than (A) that is 9 (g / 10 minutes) or less. And a heat-sealing strength between the heat-sealing layers: Hs is 7 (N / 15 mm) or more.
  • the end resistance is 30 (N / 20 mm) or more and 90 (N / 20 mm) or less in both the winding length direction (MD direction) and the width direction (direction orthogonal to the winding length direction: TD direction).
  • the polylactic acid resin film as described in any one of 1) to 5) above.
  • a film is provided. Since the polylactic acid-based resin film of the present invention is excellent in heat sealability, impact resistance, and transparency, bags for various industrial products, bags for miscellaneous goods such as CD cases, bags for foodstuffs such as vegetables and fruits, and tubes It can be preferably used for various packaging applications such as bags, pillow bags, and banding tapes.
  • the present invention has the above-mentioned problems, that is, excellent heat sealing properties, impact resistance, and transparency, particularly excellent for packaging materials, and also has excellent economical efficiency that can be manufactured with relatively inexpensive equipment. As a result of intensive studies on the film, it was the first successful solution to this problem. *
  • the composition contains 65% by mass to 95% by mass of the polylactic acid resin (A), and the composition further has a melt mass flow rate at 190 ° C. under a load of 2.16 kg. : MFR (g / 10 min) of 3 (g / 10 min) or more and 9 (g / 10 min) or less of aliphatic polyester and / or aliphatic aromatic polyester (B) other than (A) 5 It is characterized by having at least one heat seal layer comprising the composition and containing at least one mass% and not more than 35 mass%, and having a heat seal strength between the heat seal layers: Hs of 7 (N / 15 mm) or more.
  • the polylactic acid resin (A) used for the polylactic acid resin film of the present invention is preferably one containing L-lactic acid and / or D-lactic acid as a main component.
  • the main component means that the component derived from lactic acid is 70% by mass or more and 100% by mass or less in 100% by mass of the total components of the resin, and homopolylactic acid substantially consisting of L-lactic acid and / or D-lactic acid is preferable. Used.
  • the polylactic acid resin (A) used in the present invention preferably has crystallinity.
  • the polylactic acid-based resin (A) has crystallinity when the polylactic acid-based resin is sufficiently crystallized under heating and then subjected to differential scanning calorimetry (DSC) measurement in an appropriate temperature range. It means that the heat of crystal melting derived from the polylactic acid component is observed.
  • DSC differential scanning calorimetry
  • the polylactic acid resin (A) used for this invention has crystallinity, it is suitable at the point which can provide heat resistance with respect to a polylactic acid-type resin film.
  • homopolylactic acid has higher melting point and crystallinity as the optical purity is higher.
  • the melting point and crystallinity of polylactic acid are affected by the molecular weight and the catalyst used during polymerization, but normally, homopolylactic acid having an optical purity of 98% or more has a melting point of about 170 ° C. and a relatively high crystallinity. Further, as the optical purity is lowered, the melting point and crystallinity are lowered. For example, homopolylactic acid having an optical purity of 88% has a melting point of about 145 ° C., and homopolylactic acid having an optical purity of 75% has a melting point of about 120 ° C. It is. Homopolylactic acid with an optical purity lower than 70% does not show a clear melting point and is amorphous.
  • the polylactic acid-based resin (A) used in the present invention may be mixed with crystalline homopolylactic acid and amorphous homopolylactic acid for the purpose of imparting or improving necessary functions depending on the application used as a film. Is possible. In this case, the proportion of amorphous homopolylactic acid may be determined within a range that does not impair the effects of the present invention. In addition, when it is desired to impart relatively high heat resistance when a polylactic acid resin film is used, at least one of the polylactic acid resins (A) used may contain polylactic acid having an optical purity of 95% or more. preferable.
  • the mass average molecular weight of the polylactic acid resin (A) used in the present invention is usually at least 50,000, preferably 80,000 to 400,000, more preferably 100,000 to 300,000.
  • the mass average molecular weight is a molecular weight calculated by a polymethyl methacrylate conversion method after measurement with a chloroform solvent by gel permeation chromatography (GPC).
  • the mass average molecular weight of the polylactic acid-based resin (A) By setting the mass average molecular weight of the polylactic acid-based resin (A) to at least 50,000, when the composition containing the polylactic acid-based resin (A) is processed into a film, the mechanical properties are excellent. can do.
  • the polylactic acid resin (A) used in the present invention may be a copolymerized polylactic acid obtained by copolymerizing other monomer components having ester forming ability in addition to L-lactic acid and D-lactic acid.
  • copolymerizable monomer components include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and other hydroxycarboxylic acids, ethylene glycol, propylene glycol, butane Compounds containing a plurality of hydroxyl groups in the molecule such as diol, neopentyl glycol, polyethylene glycol, glycerin, pentaerythritol or derivatives thereof, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2 , 6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphospho
  • a copolymerized polylactic acid is used as the polylactic acid-based resin (A)
  • a copolymerized polylactic acid in which the component derived from lactic acid is 70% by mass or more in 100% by mass of the total component of the resin as described above is preferably used. It is done.
  • the production method of the polylactic acid resin (A) will be described in detail later, but a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.
  • the polylactic acid resin film of the present invention has at least one heat seal layer made of a composition containing 65% by mass or more and 95% by mass or less of the polylactic acid resin (A) described above.
  • the composition constituting the heat seal layer contains less than 65% by mass of the polylactic acid resin (A)
  • the ratio of the polylactic acid-type resin (A) of the composition which comprises this heat seal layer is more than 95 mass%, when it is set as a polylactic acid-type resin film, sufficient heat-sealability is not acquired.
  • the polylactic acid-type resin film of this invention contains 5 mass% or more and 35 mass% or less of aliphatic polyesters and / or aliphatic aromatic polyesters (B) other than polylactic acid other than polylactic acid-type resin (A). It has at least one heat seal layer made of the composition.
  • the heat seal layer is When the film is included, sufficient heat sealability cannot be obtained.
  • composition which comprises this heat seal layer contains aliphatic polyester and / or aliphatic aromatic polyester (B) other than polylactic acid-type resin (A) exceeding 35 mass%, (A) and ( Similarly, sufficient heat sealability cannot be obtained mainly due to the interfacial peeling of B).
  • content of (B) is preferably 10% by mass or more and 20% by mass or less of the composition constituting the heat seal layer.
  • impact resistance is also provided to the polylactic acid-type resin film of this invention which has at least 1 layer of a heat seal layer and this heat seal layer by containing (B).
  • Examples of aliphatic polyesters and / or aliphatic aromatic polyesters (B) other than polylactic acid include polyglycolic acid, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate, 3-hydroxyvalerate). , Polycaprolactone, or an aliphatic polyester comprising an aliphatic diol such as ethylene glycol or 1,4-butanediol and an aliphatic dicarboxylic acid such as succinic acid or adipic acid, or poly (butylene succinate / terephthalate), poly ( A copolymer of an aliphatic polyester such as butylene adipate and terephthalate) and an aromatic polyester.
  • polyglycolic acid poly (3-hydroxybutyrate), poly (3-hydroxybutyrate, 3-hydroxyvalerate).
  • Polycaprolactone or an aliphatic polyester comprising an aliphatic diol such as ethylene glycol or 1,4-butanediol and an aliphatic dicar
  • aliphatic polyesters and / or aliphatic aromatic polyesters (B) other than polylactic acid are polybutylene succinates and polybutylene succinates and adipates.
  • Polybutylene succinate-based resins such as polybutylene succinate and adipate are particularly preferably used.
  • MFR g / 10 min
  • JIS-K-7210 JIS-K-7210) : 1999
  • the MFR of (B) is more than 9 (g / 10 minutes) and (B) has a lower viscosity
  • the composition constituting the heat seal layer of the polylactic acid resin film of the present invention When the film is formed by the inflation method, the bubbles become unstable.
  • the polylactic acid-based resin film of the present invention comprises a polylactic acid-based resin (A) at 65 mass% to 95 mass%, a melt mass flow rate under a load of 190 ° C. and 2.16 kg: MFR (g / 10 minutes) ) Is 3 (g / 10 minutes) or more and 9 (g / 10 minutes) or less, and the aliphatic polyester and / or aliphatic aromatic polyester (B) other than (A) is 5% by mass or more and 35% by mass or less.
  • the heat seal layer is composed of at least one layer composed of a composition containing the same, but the inside may have a single-layer structure having the same composition as the heat seal layer (that is, a polylactic acid resin film composed of only the heat seal layer).
  • a laminated structure including a plurality of layers having a layer made of a composition different from the layer may be used.
  • the heat seal layer of this invention which consists of a composition containing polylactic acid-type resin (A) and aliphatic polyester and / or aliphatic aromatic polyester (B) is at least 1 layer of outermost layer. It is important that
  • the heat seal layer means a layer that can be bonded to another layer by bringing the layer into contact with another layer in a state where heat is applied.
  • the heat sealing layer in the polylactic acid resin film of the present invention is not particularly limited as long as it can be bonded to another layer by applying heat, but the heat sealing strength between the heat sealing layers: 7 (N / 15 mm) That is important.
  • the heat seal strength said here is the value measured by the method of an Example description. When the heat seal strength is less than 7 (N / 15 mm), the seal strength is practically insufficient such that the heat seal portion may be peeled off during use without breaking the film.
  • the heat seal layer of the polylactic acid-based resin film of the present invention when at least one heat seal layer of the polylactic acid-based resin film of the present invention is bonded to form a bag, there arises a problem that the heat seal portion is peeled off during use as a bag.
  • the upper limit of heat seal strength is usually 30 (N / 15mm). Therefore, the practically achievable upper limit of the heat seal strength of the heat seal layer used in the film of the present invention is considered to be about 30 (N / 15 mm), and the upper limit is 13 (N / 15 mm). ) Is sufficient from the viewpoint of use as a bag.
  • the polylactic acid in the composition constituting the heat seal layer as described above Content of the resin-based resin (A) is 65% by mass to 95% by mass, and the content of the aliphatic polyester and / or the aliphatic aromatic polyester (B) in the composition constituting the heat seal layer Of an aliphatic polyester and / or aliphatic aromatic polyester (B) at 190 ° C.
  • aliphatic polyester examples thereof include a mode in which a polybutylene succinate resin is used as the tellurium and / or aliphatic aromatic polyester (B).
  • the polylactic acid resin film of the present invention preferably has a haze of 1% or more and 10% or less, more preferably 8% or less, and even more preferably 5% or less.
  • the haze is 10% or less, the contents can be easily confirmed when molded into various packaging applications such as bags for foods such as vegetables and fruits, bags for various industrial products, etc. It is often preferable due to its high design properties.
  • the lower limit is about 1%. A lower limit of about 2% is sufficient.
  • the polylactic acid resin film of the present invention preferably has a coefficient of dynamic friction ( ⁇ d) between heat seal layers of the polylactic acid resin film of 0.5 or less. In this case, it is preferable in that it can be easily wound up without wrinkles or tarmi due to an appropriate sliding property.
  • the dynamic friction coefficient ( ⁇ d) between the heat seal layers of the polylactic acid resin film is more preferably 0.45 or less. In general, the coefficient of dynamic friction in the case of a polylactic acid-based resin film is difficult to be less than 0.1, so the lower limit is about 0.1 and the lower limit is about 0.2.
  • the polylactic acid-based resin film of the present invention has an end tear resistance of 30 (N / 20 mm) or more in both the winding length direction (MD direction) and the width direction (direction orthogonal to the winding length direction: TD direction). (N / 20 mm) or less is preferable.
  • the end-row resistance value generally has a positive correlation with the impact resistance. When the end-row resistance value is high, the end-row resistance value often has high impact resistance. If the end tear resistance is 30 (N / 20 mm) or more in both directions, it can be said that mechanical properties and impact resistance have no particular problems in general use in various packaging applications, which is a preferred application of the present invention.
  • the end resistance is 90 (N / 20 mm) or less in both directions, it is possible to manufacture with an inflation type film forming machine which is a relatively inexpensive facility, which is economically advantageous.
  • the polylactic acid-based resin film of the present invention has an end tear resistance of 35 (N / 20 mm) or more and 75 (N / 20 mm) or less in both directions, more preferably 40 (N / 20 mm) or more and 65 (N / 20 mm) or less is more preferable.
  • both the winding length direction (MD direction) and the width direction (direction orthogonal to the winding length direction: TD direction) of the polylactic acid-based resin film are directions in the film plane.
  • the end tear resistance of the polylactic acid-based resin film of the present invention is 30 (N / 20 mm) or more in the winding length direction (MD direction) and the width direction (direction perpendicular to the winding length direction: TD direction), 90 (N / 20 mm) or less, it is important to form the film while adjusting the orientation of the film.
  • the film is produced by an inflation film-forming method, or formed by an unstretched film-forming method such as a T-die casting method. Examples thereof include a method of forming a film while suppressing orientation in a biaxially stretched film forming method such as a T-die casting / biaxial stretching method or a tubular method.
  • composition constituting the heat seal layer of the polylactic acid resin film of the present invention may contain components other than those described above as long as the effects of the present invention are not impaired.
  • known antioxidants, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, antioxidants, ion exchange agents, plasticizers, crystal nucleating agents, Inorganic particles, organic particles, and organic compounds may be added as necessary as coloring pigments or lubricants.
  • the composition constituting the heat seal layer of the polylactic acid-based resin film of the present invention may be added with an organic lubricant as long as the effects of the present invention are not impaired.
  • the addition amount is usually 0.1% by mass or more and 5% by mass or less. In this case, blocking after winding can be favorably suppressed.
  • problems such as a decrease in melt viscosity and deterioration of workability due to excessive addition of an organic lubricant, or poor appearance such as bleed out and haze up when formed into a film are less likely to occur.
  • organic lubricants include liquid paraffins, natural paraffins, synthetic paraffins, aliphatic hydrocarbons such as polyethylene, stearic acid, lauric acid, hydroxystearic acid, fatty castors such as hard castor oil, stearic acid amide, oleic acid amide, Fatty acid amides such as erucic acid amide, lauric acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis lauric acid amide, fatty acid metal salts such as aluminum stearate, lead stearate, calcium stearate, magnesium stearate Long chain fatty acid esters such as fatty acid (partial) esters of polyhydric alcohols such as glycerin fatty acid esters and rubitan fatty acid esters, and long chain ester waxes such as butyl stearate and montan wax System and the like.
  • antioxidants examples include hindered phenols and hindered amines.
  • Color pigments include inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide, cyanine, styrene, phthalocyanine, anthraquinone, perinone, isoindolinone, quinophthalone, and quinocridone.
  • Organic pigments such as thioindigo can be used.
  • the particles (C) are contained in the composition constituting the heat seal layer of the polylactic acid resin film of the present invention for the purpose of improving the slipperiness and blocking resistance of the processed product, for example, inorganic
  • the particles include silicon oxide such as silica, various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate and calcium phosphate.
  • Fine particles comprising various phosphates such as magnesium phosphate, various oxides such as aluminum oxide, titanium oxide and zirconium oxide, and various salts such as lithium fluoride can be used.
  • organic particles as particles (C) to be included in the composition constituting the heat seal layer of the polylactic acid-based resin film of the present invention calcium oxalate, calcium, barium, zinc, manganese, magnesium, etc.
  • Fine particles made of terephthalate are used.
  • the crosslinked polymer particles include fine particles made of a vinyl monomer such as divinylbenzene, styrene, acrylic acid or methacrylic acid, or a copolymer.
  • organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.
  • the particles (C) to be contained in the composition constituting the heat seal layer may be selected from, for example, the above-mentioned inorganic particles and organic particles according to the purpose. In many cases, it is advantageous to select inorganic particles that have a relatively high anti-blocking effect and that are advantageous in terms of cost.
  • the average particle size of inorganic particles and organic particles suitable as the particles (C) is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 3 to 6 ⁇ m.
  • the composition constituting the heat seal layer of the polylactic acid resin film of the present invention has an average particle size of 3 to 6 ⁇ m. It is preferable to contain particles (C) (inorganic particles and / or organic particles).
  • the average particle diameter here is the cumulative median diameter (Median diameter), that is, the cumulative curve is 50% when the cumulative curve is determined with the total volume of the aggregate of powders being 100%.
  • Particle diameter (50% diameter [ ⁇ m]), which can be determined by a microtrack FRA laser particle size distribution analyzer or the like.
  • the composition constituting the heat seal layer of the polylactic acid-based resin film contains the aforementioned particles (C), particularly particles (C) having an average particle diameter of 3 to 6 ⁇ m, the content increases.
  • the film haze Ha (%) of the polylactic acid resin film to 1% or more and 10% or less
  • dynamic friction between the heat seal layers of the polylactic acid resin film Coefficient: From the viewpoint of controlling ⁇ d to 0.5 or less, it is preferably 0.05% by mass or more and 1% by mass or less in 100% by mass of the composition constituting the heat seal layer, and 0.1% by mass or more from the same viewpoint. 0.6 mass% or less is more preferable.
  • the preferable content of the aromatic aromatic polyester (B) and the particles (C) is such that (A) is 79% by mass or more and 89.95% by mass or less, and (B) is 10% by mass or more, 20% in 100% by mass of the composition. It is a preferred embodiment that the mass% or less and (C) is 0.05 mass% or more and 1 mass% or less.
  • the composition which comprises the heat seal layer of the polylactic acid resin-type film of this invention may contain a plasticizer in the range which does not impair the effect of this invention.
  • plasticizers include, for example, phthalate esters such as diethyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-1-butyl adipate, di-n-octyl adipate, di-n-butyl sebacate , Aliphatic dibasic acid esters such as di-2-ethylhexyl azelate, phosphate esters such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate, tributyl acetylcitrate, tri-2-ethylhexyl acetylcitrate , Hydroxy polycarboxylic esters such as acetyl citrate tributyl, fatty acid esters such as methyl
  • the method for calculating the solubility parameter is described in P.A. Small, J.M. Appl. Chem. 3, 71 (1953).
  • a biodegradable plasticizer is preferable from the viewpoint of keeping the biodegradability of the entire film.
  • plasticizers approved by the US Food Sanitation Agency (FDA) or the Sanitation Council for Polyolefins are preferred.
  • plasticizers include triacetin, epoxidized soybean oil, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl ester, adipic acid-based aliphatic polyester, acetyl citrate tributyl, acetyl ricinoleic acid ester, glycerin fatty acid ester, sucrose
  • plasticizers include triacetin, epoxidized soybean oil, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl ester, adipic acid-based aliphatic polyester, acetyl citrate tributyl, acetyl ricinoleic acid ester, glycerin fatty acid ester, sucrose
  • fatty acid esters sorbitan
  • the number average molecular weight is 1,000 or more. It is preferable that the plasticizer is a solid plasticizer at room temperature, such as polyethylene glycol.
  • the thickness of the polylactic acid-based resin film of the present invention is not particularly specified, but when it is formed by an inflation method, it is usually preferably a film having a thickness of 10 ⁇ m to 120 ⁇ m. If the thickness is less than 10 ⁇ m, the film may be insufficient in stiffness. Further, when the thickness exceeds 120 ⁇ m, the packaging material may be too strong, and when it is used for various packaging applications, the handling property may be inferior. In particular, in the inflation film-forming method, bubbles tend to become unstable due to their own weight. From the same viewpoint, the polylactic acid resin film of the present invention preferably has a thickness of 15 ⁇ m or more and 60 ⁇ m or less.
  • the polylactic acid-type resin film of this invention is a single unit of only the heat seal layer which consists of a composition containing the said polylactic acid-type resin (A) and the said aliphatic polyester and / or aliphatic aromatic polyester (B).
  • the thickness of the heat seal layer itself matches the thickness of the polylactic acid resin film, that is, the thickness of the heat seal layer is preferably 10 ⁇ m or more and 120 ⁇ m or less, and 15 ⁇ m or more and 60 ⁇ m or less. It is more preferable that
  • the ratio of the thickness of the heat seal layer to the total thickness of the polylactic acid resin film is 100%. (%) Is not particularly defined, but from the viewpoint of film formation stability, the ratio of the thickness of the heat seal layer to the total thickness of 100% is usually from 5% to 95%, preferably from 10% to 90%.
  • the polylactic acid-based resin film of the present invention has a reduced strength due to hydrolysis of the polylactic acid-based resin, particularly in applications that do not require biodegradability, such as packaging for various industrial products, or where it is preferable to have storage durability.
  • the carboxyl group terminal concentration in the heat seal layer of the film is preferably 0 equivalent / 10 3 kg or more and 30 equivalent / 10 3 kg or less, more preferably It is 20 equivalents / 10 3 kg or less, more preferably 10 equivalents / 10 3 kg or less.
  • the carboxyl group terminal concentration in the heat seal layer of the film is 30 equivalents / 10 3 kg or less
  • the carboxyl group terminal concentration, which also serves as a hydrolysis autocatalyst is sufficiently low. In many cases, it is possible to impart such durability.
  • Examples of the method for setting the carboxyl group terminal concentration in the heat seal layer of the film to 30 equivalents / 10 3 kg or less include, for example, a method of controlling by a catalyst or heat history during synthesis of the polylactic acid resin (A), the heat Examples thereof include a method of reducing a heat history such as lowering an extrusion temperature at the time of film formation including a seal layer or shortening a residence time, a method of blocking a carboxyl group terminal using a reactive compound, and the like.
  • the method of blocking the carboxyl group terminal using a reactive compound it is preferable that at least a part of the carboxyl group terminal in the heat seal layer of the film is blocked, and it is more preferable that the whole amount is blocked.
  • reactive compounds include condensation reactive compounds such as aliphatic alcohols and amide compounds, and addition reactive compounds such as carbodiimide compounds, epoxy compounds, and oxazoline compounds, but extra by-products are generated during the reaction.
  • An addition reaction type compound is preferable in terms of difficulty, and a carbodiimide compound is particularly preferable from the viewpoint of reaction efficiency.
  • the polylactic acid resin (A) in the present invention can be obtained, for example, by the following method.
  • the main component is a lactic acid component of L-lactic acid or D-lactic acid, and a hydroxycarboxylic acid other than the lactic acid component described above can be used in combination.
  • a cyclic ester intermediate of hydroxycarboxylic acid for example, lactide, glycolide, etc. can be used as a raw material.
  • dicarboxylic acids and glycols can also be used.
  • the polylactic acid resin (A) can be obtained by a method of directly dehydrating and condensing the raw materials or a method of ring-opening polymerization of the cyclic ester intermediate.
  • lactic acid or lactic acid and hydroxycarboxylic acid are preferably subjected to azeotropic dehydration condensation in the presence of an organic solvent, particularly a phenyl ether solvent, and particularly preferably a solvent distilled by azeotropic distillation.
  • a polymer having a high molecular weight can be obtained by polymerizing by a method in which water is removed from the solvent and the solvent is brought into a substantially anhydrous state and returned to the reaction system.
  • a high molecular weight polymer can be obtained by subjecting a cyclic ester intermediate such as lactide to ring-opening polymerization under reduced pressure using a catalyst such as tin octylate.
  • a method for adjusting the conditions for removing moisture and low molecular weight compounds during heating and refluxing in an organic solvent, a method for suppressing the depolymerization reaction by deactivating the catalyst after completion of the polymerization reaction, and a method for heat-treating the produced polymer Can be used to obtain a polymer with a small amount of lactide.
  • dissolved each component in the solvent is used. It is possible to produce a composition by removing the solvent after uniform mixing, but there is no need for steps such as dissolution of the raw material in the solvent and removal of the solvent. It is preferable to adopt a melt-kneading method for producing the composition by doing so.
  • the melt kneading method is not particularly limited, and a commonly used known mixer such as a kneader, roll mill, Banbury mixer, single-screw or twin-screw extruder can be used. Among these, from the viewpoint of productivity, it is preferable to use a single screw or twin screw extruder.
  • the temperature at the time of melt kneading is preferably in the range of 150 ° C. to 240 ° C., and more preferably in the range of 200 ° C. to 220 ° C. in order to prevent the deterioration of the polylactic acid resin (A).
  • the polylactic acid resin film of the present invention can be obtained, for example, by a known film production method such as a known inflation method or T-die casting method using the composition obtained by the above-described method.
  • the inflation method is preferably employed in order to provide the object of the present invention, in particular, to provide excellent properties at the same time as the packaging material, and at the same time to provide high economic efficiency.
  • the chip is kept at 60 to 110 ° C. It is preferable to use after setting the moisture content to 500 ppm or less by drying for 6 hours or more. Furthermore, by carrying out vacuum drying under a high vacuum with a degree of vacuum of 10 Torr or less, the lactide content in the composition containing the polylactic acid resin (A) and the like is reduced, thereby preventing hydrolysis during melt-kneading.
  • the polylactic acid-based resin film of the present invention is produced by an inflation method, for example, the polylactic acid-based resin (A) adjusted to have a desired ratio and the aliphatic polyester and / or the aliphatic aromatic polyester (B).
  • the dry blend is melt-extruded with a twin-screw extruder with a vacuum vent hole, led to an annular die, extruded from the annular die, and supplied with dry air to form a balloon (bubble). After air-cooling and solidification, folding at a predetermined take-up speed while being folded flat with a nip roll, both ends or one end may be cut open as necessary.
  • the annular die is a spiral type. It is good to use.
  • the extrusion temperature of the composition containing the polylactic acid resin (A) or the like is usually in the range of 150 to 240 ° C., but the temperature of the annular die is important for improving the thickness accuracy and uniformity.
  • the temperature of the annular die is in the range of 150 to 190 ° C, preferably 150 to 170 ° C. If the temperature of the annular die is less than 150 ° C., the temperature at which the composition is extruded is too low, the molding behavior at the time of blow-up immediately after discharge becomes uneven, the thickness accuracy deteriorates, and the winding shape becomes poor.
  • the temperature of the annular die is more preferably 160 to 170 ° C.
  • the blow ratio of the bubble depends on the relationship between the discharge amount and the take-up speed of the nip roll, but the film may be anisotropic if it is too low or too high. It tends to be unstable and is usually in the range of 2.0 to 4.0.
  • various surface treatments may be applied for the purpose of improving printability, laminate suitability, coating suitability, and the like.
  • the surface treatment include corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc., and any method can be used, but continuous treatment is possible, and equipment for existing film forming equipment is used.
  • Corona discharge treatment can be exemplified as the most preferable because of its easy installation and simple processing.
  • the polylactic acid resin film of the present invention is excellent in heat sealability, impact resistance, and transparency, it is particularly suitable for packaging materials.
  • the polylactic acid resin film of the present invention can be used as various bags by processing.
  • One of the bags according to the present invention is characterized in that the surface of the heat-seal layer of the polylactic acid resin film of the present invention and a non-woven fabric mainly composed of the polylactic acid resin have a side directly bonded. It is a bag to do.
  • having a directly bonded side means that at least one side of the bag has a surface of the heat seal layer of the polylactic acid-based resin film and a non-woven fabric mainly composed of the polylactic acid-based resin without using an adhesive or the like. And are attached.
  • the nonwoven fabric used in the bag of the present invention is obtained by a conventional method, and the production method is not particularly limited. For example, those obtained by a spun bond method or a melt blow method can be suitably used. It is important that the nonwoven fabric is mainly composed of a polylactic acid resin. By having a polylactic acid-based resin as a main component, good heat-sealability with the polylactic acid-based resin film of the present invention is exhibited.
  • the polylactic acid-type resin which comprises a nonwoven fabric can use resin similar to the above-mentioned polylactic acid-type resin (A).
  • the main component in the nonwoven fabric mainly composed of a polylactic acid resin means that the polylactic acid resin is contained in an amount of 50% by mass or more and 100% by mass or less in 100% by mass of the total resin composition constituting the nonwoven fabric.
  • the surface of the heat seal layer of the polylactic acid resin film and the nonwoven fabric mainly composed of the polylactic acid resin are overlapped, at least one side is heat sealed,
  • the surface of the heat seal layer of the resin film and the nonwoven fabric mainly composed of polylactic acid resin can be obtained by providing a directly bonded side, but it is important that the heat seal location has at least one side, Alternatively, three-side heat sealing may be performed.
  • three-side heat sealing may be performed.
  • At least one side is a bag characterized in that the polylactic acid resin film of the present invention is directly bonded.
  • the bag of this embodiment is characterized in that at least one side is bonded by heat sealing using the polylactic acid resin film of the present invention without using a non-woven fabric.
  • directly bonded means that at least one side of the bag is bonded to each other without interposing an adhesive or the like.
  • a bag of this aspect for example, two sheets of the polylactic acid-based resin film of the present invention are prepared, and at least one heat seal layer is overlapped with another film, and at least one side is heat sealed, The other two sides can be sealed with an adhesive or the like, or the other two sides can be heat sealed to obtain a bag.
  • a bag can also be obtained by preparing one sheet of the polylactic acid-based resin film of the present invention, folding it back and heat-sealing two sides.
  • FIG. 1 Another bag of the present invention is a bag characterized in that at least one side of the tube-shaped polylactic acid resin film of the present invention is directly bonded.
  • the fact that at least one side of the bag obtained by using the tube-shaped polylactic acid resin film does not pass through an adhesive or the like between the polylactic acid resin films. It means that it is adhered.
  • the polylactic acid resin film of the present invention can be formed into a tube shape and then adhered by heat sealing at least one side.
  • a general inflation method or a tubular stretching method can be suitably applied as a method for forming a seamless tube-like film.
  • the polylactic acid-based resin film of the present invention can also be suitably used as a banding tape used when bundling PTP (press-through pack) packaging of drugs and the like.
  • the polylactic acid-based resin film of the present invention is prepared, for example, by preparing two sheets of the polylactic acid-based resin film of the present invention so that these heat seal layers face each other, and further bonding three sides by heat sealing, By putting a pillow from the remaining one side, it can be suitably used as a pillow bag.
  • melt mass flow rate MFR (g / 10 min) In accordance with JIS-K-7210 (1999), melt mass flow rate value: MFR (g / 10 min) of aliphatic polyester and / or aliphatic aromatic polyester under a load of 190 ° C. and 2.16 kg was determined.
  • Heat seal strength between heat seal layers Hs (N / 15 mm) A strip-shaped measurement sample having a width of 15 mm was prepared with the measurement direction (MD direction) as the long side.
  • Heat seal tester TP-701S made by tester industry, hot plate shape: flat metal / rubber (one side heating), hot plate temperature: 120 ° C, surface pressure: 1kgf / cm 2 , seal Time: Create a test sample in 1 second and use “Tensilon Universal Testing Machine” UTC-100 type manufactured by Orientec Co., Ltd., peeling direction: MD direction, peeling speed: 200 mm / min. Heat seal strength: Hs (N / 15 mm) was determined. The measurement was performed 5 times for each level, and the average value of the 5 measurements was obtained.
  • ⁇ d resistance value / load (5) End crack resistance in the winding length direction and width direction (direction orthogonal to the winding length direction)
  • the winding length direction is the longitudinal direction.
  • a direction was cut into a strip with a width of 20 mm, and measured with a Tensilon tensile tester according to JIS-C-2111 (2002). The sample was passed through a V-shaped jig set in a tensile tester and pulled at a speed of 200 mm / min to obtain the stress (N / 20 mm) when the sample was torn.
  • the width direction it was cut into a strip shape having a width of 20 mm with the width direction as a longitudinal direction, and measurement was performed in the same manner as described above.
  • (6) Wrinkles and Tarmi After storing the roll sample for 3 days in an atmosphere of temperature 23 ° C. and humidity 65% RH, an iron shaft with a diameter smaller than the inner diameter of the paper tube is passed through the paper tube of the roll sample, and both ends of the iron shaft The roll was placed in a state where it was hooked horizontally and freely rotated, the film was unwound from the roll sample by about 2 m in the horizontal direction, visually observed, and judged according to the following criteria.
  • Examples 3 and 8, Comparative Example 1 An SL1 master chip prepared by melt-kneading the polylactic acid PL2 as a base chip in advance so as to be inorganic particles SL1: 30% by mass was prepared. In addition to polylactic acid and aliphatic polyester, an SL1 master chip was used, and a mixture in which each component had a ratio shown in Table 1 was used (for example, in Comparative Example 1, polylactic acid PL2: 98.3% by mass). And a SL1 master chip: a mixture of 1.7% by mass), a film having a final thickness of 25 ⁇ m was obtained in the same manner as in Example 1. The film formation was stable without breaking for 2 hours. The evaluation results of the obtained film are shown in Table 1.
  • Example 6 In advance, an SL2 master chip prepared by melt-kneading the polylactic acid PL2 as a base chip to be inorganic particles SL2: 30% by mass was prepared. In addition to polylactic acid and aliphatic polyester, an SL2 master chip was used, and a mixture in which each component had a ratio shown in Table 1 was used (polylactic acid PL2: 98.3 mass% and SL2 master chip: 1. A film having a final thickness of 25 ⁇ m was obtained in the same manner as in Example 1 except that the mixture was 7% by mass. The film formation was stable without breaking for 2 hours. The evaluation results of the obtained film are shown in Table 1.
  • Example 7 Comparative Example 5
  • a polylactic acid, aliphatic polyester, SL1 master chip prepared in the same manner as in Comparative Example 1 and the like, and using a mixture in which each component has a ratio shown in Table 1, respectively, by a T-die cast biaxial stretching method A film was formed. That is, the above mixture is supplied to a single screw extruder having a cylinder temperature of 190 to 210 ° C. and a screw diameter of 65 mm, extruded from a T die having a width of 300 mm, a lip clearance of 1.0 mm and a temperature of 190 ° C., and cast to a mirror drum having a temperature of 25 ° C.
  • the polylactic acid-based resin films of Examples 1 to 9 were excellent in heat sealability and were of a quality having no practical problems such as haze, roll wrinkles, and tarmi.
  • Comparative Examples 1 to 6 do not contain an aliphatic polyester (Comparative Examples 1 and 5), but contain an aliphatic polyester, but are MFRs outside the scope of the present invention (Comparative Examples 2 and 3). Since the content is outside the range of the present invention (Comparative Examples 4 and 6), the heat sealability was insufficient.
  • Example 10 A film obtained in the same manner as in Example 3 and a polylactic acid non-woven fabric having a basis weight of 40 g were overlapped and cut into a square having a side of 125 mm. / Cm 2 , seal time: 1 second, seal width: 2 mm, and bonded by heat sealing to prepare a bag sample having a film on one side and a nonwoven fabric on one side.
  • Example 11 A mixture of polylactic acid and aliphatic polyester in the same proportions as in Example 3 described in Table 1 was supplied to a single screw extruder having a cylinder temperature of 190 to 210 ° C.
  • This tubular film was cut into a length of 470 mm in the winding length direction, and one side of the cut portion was heated at a plate temperature of 130 ° C., a surface pressure of 1 kgf / cm 2 , a seal time of 1 second, and a seal width.
  • the prepared sample had a good appearance including the seal part, and I tried putting one 500 ml PET bottle filled with the contents, but there was no problem in carrying around without removing the bottom.
  • Example 12 In the same manner as in Example 3, the film obtained by changing only the final thickness to 30 ⁇ m by adjusting the discharge amount was slit to a width of 40 mm, and an automatic banding machine manufactured by Omori Machine Industry Co., Ltd .: BM-510 type was used. A banding packaging sample of 10 bundles of PTP (press-through pack) packaging was prepared.
  • Example 13 The film obtained in the same manner as in Example 3 was slit into a width of 210 mm, and a product made by Fujikikai Corporation, a forward pillow packaging machine (horizontal pillow packaging type): FW3200 / B type, frontage 92 mm, cut length 190 mm, The center seal was a palm type, the width was 13 mm, and the seal width of the frontage was 13 mm.
  • a set temperature of the heat seal roll for the center seal was set to 130 ° C.
  • a set temperature of the front seal bar was set to 140 ° C.
  • bags were made at a rate of 100 bags / minute to prepare pillow package samples.
  • the prepared sample, including the seal part, was free of wrinkles and tarnish, had a good appearance, had good visibility of the contents, and had no problem in practical use in terms of the strength of the seal part.
  • the present invention is applied as a packaging material application.
  • the heat seal layer of the present invention it is suitable as various bags.
  • the polylactic acid-based resin film of the present invention is an excellent polylactic acid-based resin film excellent in heat sealability, impact resistance, transparency, and suitable for the inflation method, which is a relatively inexpensive facility. It can be preferably used for various packaging applications such as bags for industrial products, bags for miscellaneous goods such as CD cases, food bags such as vegetables and fruits, tube bags, pillow bags, and banding tapes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film de résine d’acide polylactique qui présente des propriétés de scellement à chaud, une résistance aux chocs et une transparence excellentes, qui est très approprié pour être utilisé comme matériau d’emballage, qui est en outre approprié pour être utilisé dans un procédé d’insufflation à l’aide d’un équipement relativement peu cher, et qui est très rentable. Le film de résine d’acide polylactique est caractérisé en ce que le film de résine d’acide polylactique comprend au moins une couche thermocollante d’une composition ne contenant pas moins de 65 % en masse et pas plus de 95 % en masse d’une résine d’acide polylactique (A) et pas moins de 5 % en masse et pas plus de 35 % en masse d’un polyester aliphatique (autre que la résine d’acide polylactique (A)) et/ou d’un polyester aromatique aliphatique (B) qui ont un taux d’écoulement à l’état fondu (MFR (g/10 min)) non inférieur à 3 (g/10 min) et non supérieur à 9 (g/10 min) dans des conditions de température de 190°C et de charge de 2,16 kg, et en ce qu’il présente une résistance au thermocollage entre les couches thermocollantes (Hs) non inférieure à 7 (N/15 mm).
PCT/JP2009/062495 2008-07-10 2009-07-09 Film de résine d’acide polylactique WO2010005043A1 (fr)

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CN102892817A (zh) * 2010-06-21 2013-01-23 东丽株式会社 聚乳酸系膜
JPWO2021002207A1 (ja) * 2019-07-03 2021-09-13 Dic株式会社 積層フィルム及び蓋材

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CN107151424A (zh) * 2016-03-04 2017-09-12 汉达精密电子(昆山)有限公司 聚乳酸膜材料及其产品
TWI765551B (zh) * 2021-01-29 2022-05-21 南亞塑膠工業股份有限公司 可熱封聚酯膜

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JP2003160202A (ja) * 2001-11-22 2003-06-03 Unitika Ltd 生分解性ごみ袋
JP2003183483A (ja) * 2001-12-25 2003-07-03 Unitika Ltd 生分解性肥料袋
JP2004099670A (ja) * 2002-09-06 2004-04-02 Unitika Ltd 生分解性フィルムおよびその製造方法
JP2005313998A (ja) * 2004-04-02 2005-11-10 Asahi Kasei Life & Living Corp 生分解性袋状製品

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KR100515274B1 (ko) * 1997-11-14 2005-09-15 미쓰비시 쥬시 가부시끼가이샤 생분해성 필름 및 그 제조방법
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JP2002273845A (ja) * 2001-03-16 2002-09-25 Unitika Ltd 生分解性積層フィルム
JP2003160202A (ja) * 2001-11-22 2003-06-03 Unitika Ltd 生分解性ごみ袋
JP2003183483A (ja) * 2001-12-25 2003-07-03 Unitika Ltd 生分解性肥料袋
JP2004099670A (ja) * 2002-09-06 2004-04-02 Unitika Ltd 生分解性フィルムおよびその製造方法
JP2005313998A (ja) * 2004-04-02 2005-11-10 Asahi Kasei Life & Living Corp 生分解性袋状製品

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Publication number Priority date Publication date Assignee Title
CN102892817A (zh) * 2010-06-21 2013-01-23 东丽株式会社 聚乳酸系膜
CN102892817B (zh) * 2010-06-21 2016-12-28 东丽株式会社 聚乳酸系膜
JPWO2021002207A1 (ja) * 2019-07-03 2021-09-13 Dic株式会社 積層フィルム及び蓋材

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