WO2011162046A1 - ポリ乳酸系フィルム - Google Patents
ポリ乳酸系フィルム Download PDFInfo
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- WO2011162046A1 WO2011162046A1 PCT/JP2011/061286 JP2011061286W WO2011162046A1 WO 2011162046 A1 WO2011162046 A1 WO 2011162046A1 JP 2011061286 W JP2011061286 W JP 2011061286W WO 2011162046 A1 WO2011162046 A1 WO 2011162046A1
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- polylactic acid
- resin
- film
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- segment
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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
- 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
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
-
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a polylactic acid film excellent in flexibility, tear resistance and impact resistance, and excellent in blocking resistance and bleed-out resistance, and particularly exhibiting a good effect by an inflation film forming method.
- Patent Document 1 discloses a film having a crystalline polylactic acid resin, a plasticizer, and a crystal nucleating agent as essential components, and defining thermal characteristics.
- Patent Document 2 a crystallization treatment is applied to a film containing a polylactic acid resin composed of weakly crystalline or amorphous polylactic acid or crystalline polylactic acid, a plasticizer, and an antifogging agent.
- Patent Document 3 discloses a film comprising a composition containing a polylactic acid-based resin and a plasticizer and defining elongation, thickness, and heat shrinkage rate.
- Patent Document 1 and Patent Document 2 described above do not have sufficient blocking resistance and bleed-out resistance, and do not disclose any technique for improving the tear resistance and impact resistance of the film. .
- Patent Document 3 has excellent blocking resistance and bleed out resistance, but does not disclose any technique related to improvement of tear resistance.
- polylactic acid-based films that are excellent in flexibility, tear resistance, impact resistance, excellent in blocking resistance, and bleed-out resistance, and that are particularly effective in the inflation film forming method. However, it has not been achieved yet.
- the present invention is a polylactic acid which is excellent in tear resistance and impact resistance, and excellent in blocking resistance and bleed out resistance, and in particular, a good effect is obtained by an inflation film forming method. System film.
- the polylactic acid-based film of the present invention is a polylactic acid-based film made of a composition containing a resin (A), a resin (B), and a plasticizer (C), wherein the resin (A) is a polylactic acid-based resin,
- the resin (B) is an aliphatic polyester-based resin and / or an aliphatic aromatic polyester-based resin other than the polylactic acid-based resin, and cooled at a rate of 20 ° C./min from the melted state with a differential scanning calorimeter Polylactic acid-based film having at least one crystallization peak in the temperature range of 105 to 160 ° C., and the total calorific value of the crystallization peak in the temperature range of 105 to 160 ° C. being ⁇ Hmc A It is.
- the polylactic acid film of the present invention is a block copolymer in which the plasticizer (C) has a polyether segment and a polylactic acid segment, and / or a block copolymer having a polyester segment and a polylactic acid segment. It is preferable that
- the resin (B) is preferably at least one selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, and polybutylene adipate terephthalate.
- the polylactic acid film of the present invention preferably has a melt viscosity of 400 to 1,000 Pa ⁇ s at a temperature of 200 ° C. and a shear rate of 100 sec ⁇ 1 of the resin (B).
- the resin (B) is polybutylene adipate terephthalate, and the polybutylene adipate terephthalate has a melt viscosity of 600 to 700 Pa ⁇ s at a temperature of 200 ° C. and a shear rate of 100 sec ⁇ 1 . Is preferred.
- Polylactic acid-based film of the present invention elongation of the length and width directions at 5 ° C. (length direction perpendicular to the direction) of the (%) and the average value E L, the length and width directions at 23 ° C. mean value E H of elongation (%) is preferably the following conditions are met.
- the polylactic acid-based film of the present invention comprises at least one selected from the group consisting of melamine compounds, phenylphosphonic acid metal salts, benzenecarboxamide derivatives, talc, clay, mica, and carbon black, with a total amount of 100 mass of the composition.
- % Is preferably contained in an amount of 0.1 to 20% by mass.
- the resin (A) is preferably a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin.
- the polylactic acid-based film of the present invention preferably has a tensile modulus in the length direction and the width direction of 100 to 1,500 MPa.
- a polylactic acid film excellent in flexibility, tear resistance, impact resistance, excellent in blocking resistance and bleed-out resistance, and particularly effective in the inflation film-forming method Is done.
- the polylactic acid-based film of the present invention is mainly used for agricultural and forestry applications such as agricultural multi-films and pine worm fumigation sheets that require flexibility, tear resistance, and impact resistance, garbage bags, compost bags, or vegetables It can be preferably used for various packaging applications such as bags for foods such as fruits and fruits and bags for various industrial products.
- the present invention is a polylactic acid film excellent in the above-mentioned problems, that is, excellent in flexibility, tear resistance and impact resistance, and excellent in blocking resistance and bleed-out resistance, and in particular, good effects are exhibited by the inflation film forming method.
- the position of the crystallization peak and the calorific value when the composition is cooled at a rate of 20 ° C./min from the melted state with a differential scanning calorimeter are determined. This is the first successful solution to this problem by keeping it within certain conditions.
- the present invention is a polylactic acid film comprising a composition containing a resin (A), a resin (B), and a plasticizer (C), wherein the resin (A) is a polylactic acid resin and the resin (B) is a polylactic acid.
- Aliphatic polyester resins and / or aliphatic aromatic polyester resins other than lactic acid resins and a temperature of 105 to 160 ° C. when cooled from a molten state at a rate of 20 ° C./min with a differential scanning calorimeter
- the polylactic acid film has at least one crystallization peak in the region and satisfies the following condition when the total calorific value of the crystallization peak in the temperature region of 105 to 160 ° C. is ⁇ Hmc A.
- the polylactic acid film of the present invention is composed of a composition containing the resin (A).
- the resin (A) means a polylactic acid resin.
- the polylactic acid-based resin is a polymer having an L-lactic acid unit and / or a D-lactic acid unit as main constituent components.
- the main component means that the ratio of lactic acid units is the largest in 100 mol% of all monomer units in the polymer, and preferably 70 to 70% of lactic acid units in 100 mol% of all monomer units. 100 mol%.
- poly-L-lactic acid as used in the present invention refers to those in which the content of L-lactic acid units is more than 50 mol% and not more than 100 mol% in 100 mol% of all lactic acid units in the polylactic acid polymer.
- poly-D-lactic acid as used in the present invention refers to those having a D-lactic acid unit content of more than 50 mol% and not more than 100 mol% in 100 mol% of all lactic acid units in the polylactic acid polymer.
- Poly L-lactic acid changes in the crystallinity of the resin itself depending on the content ratio of the D-lactic acid unit. That is, if the content ratio of D-lactic acid units in poly-L-lactic acid increases, the crystallinity of poly-L-lactic acid decreases and approaches amorphous, and conversely the content ratio of D-lactic acid units in poly-L-lactic acid. As the amount decreases, the crystallinity of poly-L-lactic acid increases. Similarly, the crystallinity of the resin itself of poly D-lactic acid varies depending on the content ratio of L-lactic acid units.
- the content ratio of the L-lactic acid unit in the poly L-lactic acid used in the present invention, or the content ratio of the D-lactic acid unit in the poly D-lactic acid used in the present invention is a viewpoint for maintaining the mechanical strength of the composition. From 100 to 100 mol% of all lactic acid units, 80 to 100 mol% is preferable, and 85 to 100 mol% is more preferable.
- the crystalline polylactic acid resin referred to in the present invention is a case where the polylactic acid resin is sufficiently crystallized under heating and then measured with a differential scanning calorimeter (DSC) in an appropriate temperature range.
- DSC differential scanning calorimeter
- the amorphous polylactic acid resin referred to in the present invention refers to a polylactic acid resin that does not exhibit a clear melting point when measured in the same manner.
- the resin (A) is preferably a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin.
- the polylactic acid resin used in the present invention may be copolymerized with other monomer units other than lactic acid.
- Other monomers include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthal
- the copolymerization amount of the other monomer units is preferably 0 to 30 mol%, preferably 0 to 10 mol%, based on 100 mol% of the whole monomer units in the polymer of the polylactic acid resin. Is more preferable. In addition, it is preferable to select the component which has biodegradability among the above-mentioned monomer units according to a use.
- the main component of the polylactic acid resin used in the present invention is poly L-lactic acid
- poly D-lactic acid is mixed
- a small amount of poly L-lactic acid is mixed. It is also preferable.
- the stereocomplex crystal formed thereby functions as a crystal nucleating agent described later, and the transparency of the film can be maintained as compared with the case where a crystal nucleating agent described later is added.
- the mass average molecular weight of the polylactic acid mixed in a small amount is preferably smaller than the mass average molecular weight of the main component polylactic acid from the viewpoint of efficiently forming a stereocomplex crystal.
- the mass average molecular weight of the polylactic acid mixed in a small amount is preferably 0.5 to 50%, more preferably 1 to 40%, more preferably 2 to 30% of the mass average molecular weight of the main component polylactic acid. More preferably.
- the polylactic acid resin used in the present invention is preferably a polylactic acid block copolymer composed of a segment composed of L-lactic acid units and a segment composed of D-lactic acid units, from the viewpoint of improving heat resistance.
- the polylactic acid block copolymer since the polylactic acid block copolymer forms a stereocomplex crystal in the molecule, the melting point is higher than that of a normal crystal.
- the segment length should satisfy Y ⁇ X / 2 with respect to the mass average molecular weight X of the polylactic acid block copolymer and the maximum mass average molecular weight Y of one segment. preferable.
- the mass average molecular weight of the polylactic acid resin used in the present invention is preferably 50,000 to 500,000, more preferably 80,000 to 400,000 in order to satisfy practical mechanical properties. More preferably, it is ⁇ 300,000.
- the mass average molecular weight as used herein refers to a molecular weight calculated by a polymethyl methacrylate conversion method after measurement with a chloroform solvent by gel permeation chromatography (GPC).
- polylactic acid-based resin As a method for producing the polylactic acid-based resin, details will be described 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 film of the present invention preferably contains 30 to 95% by mass of the resin (A) in 100% by mass of the entire composition constituting the polylactic acid film. That is, it is preferable that 30 to 95% by mass of the polylactic acid resin is contained in 100% by mass of the total composition.
- the resin (A) (polylactic acid resin) By setting the resin (A) (polylactic acid resin) to 30% by mass or more in 100% by mass of the whole composition, the composition has excellent tear resistance and impact resistance, and has a biomass degree (of plant-derived raw materials). The content ratio) is increased, and the resin (A) (polylactic acid resin) is 95% by mass or less, so that the flexibility is excellent.
- the resin (A) polylactic acid-based resin
- the resin (B) is more preferably 35 to 90% by mass, and further preferably 40 to 85% by mass.
- Resin (B) aliphatic polyester resin and / or aliphatic aromatic polyester resin other than polylactic acid resin
- the resin (B) is an aliphatic polyester resin and / or an aliphatic aromatic polyester resin other than the polylactic acid resin.
- resin (B) also has biodegradability for the biodegradability expression of a film.
- aliphatic polyester resins other than polylactic acid resins include polyglycolic acid, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-3hydroxyvalerate), polycaprolactone, or ethylene glycol.
- An aliphatic polyester comprising an aliphatic diol such as 1,4-butanediol and an aliphatic dicarboxylic acid such as succinic acid or adipic acid is preferably used.
- poly (butylene succinate / terephthalate), poly (butylene adipate / terephthalate) and the like are preferably used.
- the resin (B) is selected from the group consisting of polybutylene succinate, polybutylene succinate adipate and polybutylene adipate terephthalate because it has a great effect of improving flexibility, tear resistance and impact resistance. At least one selected is more preferably used.
- Polybutylene adipate terephthalate which is an aliphatic aromatic polyester, has the highest effect of improving flexibility, tear resistance, and impact resistance.
- Resin (B) (aliphatic polyester resin and / or aliphatic aromatic polyester resin other than polylactic acid resin) contained in the polylactic acid film of the present invention is the entire composition constituting the polylactic acid film. It is preferably 5 to 45% by mass in 100% by mass. When it is 5% by mass or more, it is easy to obtain an effect of improving flexibility, tear resistance, and impact resistance. When it is 45% by mass or less, mainly in a field that requires biodegradability particularly in agricultural and forestry applications, It is preferable in that moderate biodegradability can be imparted and the degree of biomass becomes high.
- the resin (B) (aliphatic polyester-based resin and / or aliphatic aromatic polyester-based resin other than the polylactic acid-based resin) is 10 to 40% by mass in 100% by mass of the total composition, More preferably, the content is 35% by mass.
- the polylactic acid film of the present invention is composed of a composition containing a plasticizer (C) mainly for imparting flexibility.
- plasticizer (C) used in the present invention examples include phthalate esters such as diethyl phthalate, dioctyl phthalate and dicyclohexyl phthalate, di-1-butyl adipate, di-n-octyl adipate, and sebacic acid.
- Aliphatic dibasic acid esters such as di-n-butyl and di-2-ethylhexyl azelate, phosphoric acid esters such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate, tributyl acetylcitrate, acetylcitric acid Hydroxypolycarboxylic acid esters such as tri-2-ethylhexyl and acetyltributyl citrate, fatty acid esters such as methyl acetylricinoleate and amyl stearate, polyhydric alcohol esters such as glycerol triacetate and triethylene glycol dicaprylate
- Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed fatty acid butyl ester, octyl epoxy stearate, polyester plasticizers such as polypropylene glycol sebacate, polyalkylene
- the solubility parameter: SP of all plasticizers (C) contained in the composition constituting the polylactic acid-based film is (16 To 23) 1/2 MJ / m 3 is preferable, and (17 to 21) 1/2 MJ / m 3 is more preferable.
- the solubility parameter can be calculated by the method shown in P. Small, J. Appl. Chem., 3, 71 (1953).
- a biodegradable plasticizer is preferable from the viewpoint of maintaining the biodegradability of the entire film.
- plasticizer (C) approved from the above.
- plasticizer (C) examples include triacetin, epoxidized soybean oil, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl ester, adipic acid aliphatic polyester, acetyl citrate tributyl, acetyl ricinoleic acid ester, glycerin fatty acid ester Sucrose fatty acid ester, sorbitan fatty acid ester, adipic acid dialkyl ester, bis (alkyldiglycol) adipate or polyethylene glycol.
- the plasticizer (C) used in the present invention is, for example, a normal temperature (20 such as polyethylene glycol having a number average molecular weight of 1,000 or more. (° C. ⁇ 15 ° C.) in solid form, that is, the melting point is preferably higher than 35 ° C.
- 150 degreeC is an upper limit at the point which matches melt processing temperature with aliphatic polyester-type resin other than polylactic acid-type resin and polylactic acid-type resin, and / or aliphatic aromatic polyester-type resin.
- the plasticizer (C) used in the present invention is a block copolymer having a polyether segment and a polylactic acid segment, and / or a block copolymer having a polyester segment and a polylactic acid segment. More preferably, it is a coalescence.
- the plasticizing component is a polyether segment or a polyester segment.
- the mass ratio of the polylactic acid segment contained in the block copolymer plasticizer is preferably 50% by mass or less of the entire block copolymer plasticizer, since a desired flexibility can be imparted with a smaller amount of addition, preferably 5 mass. % Or more is preferable from the viewpoint of suppressing bleed-out.
- the number average molecular weight of the polylactic acid segment in one molecule of the block copolymer plasticizer is preferably 1,200 to 10,000. When the polylactic acid segment of the block copolymer plasticizer is 1,200 or more, sufficient affinity is produced between the block copolymer plasticizer and the resin (A) (polylactic acid resin).
- a part of the segment is taken into the crystal formed from the resin (A) (polylactic acid resin) and forms a so-called eutectic so as to connect the plasticizer (C) to the resin (A).
- the number average molecular weight of the polylactic acid segment of the block copolymer plasticizer is more preferably 1,500 to 6,000, and further preferably 2,000 to 5,000.
- the polylactic acid segment contained in the block copolymer plasticizer is such that L-lactic acid is 95 to 100% by mass or D-lactic acid is 95 to 100% by mass, and bleeding out is particularly suppressed. Therefore, it is preferable.
- the block copolymer plasticizer has a polyether-based and / or polyester-based segment, but the block copolymer having a polyether-based segment and a polylactic acid segment has a desired flexibility with a small amount of addition. It is preferable from a viewpoint which can provide. Furthermore, in a block copolymer having a polyether-based segment and a polylactic acid segment, it is more preferable to have a segment composed of a polyalkylene ether as a polyether-based segment from the viewpoint of imparting desired flexibility with a smaller amount of addition. preferable.
- examples of the polyether-based segment include a segment made of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol / polypropylene glycol copolymer, and the like.
- a segment made of polyethylene glycol is a resin (A ) (Polylactic acid-based resin) has a high affinity and is excellent in reforming efficiency, and is particularly preferable because a desired flexibility can be imparted by adding a small amount of plasticizer (C).
- the block copolymer plasticizer has a segment composed of a polyalkylene ether
- the polyalkylene ether segment tends to be easily oxidized or thermally decomposed when heated at the time of molding, etc. It is preferable to use a hindered amine-based antioxidant or a phosphorus-based heat stabilizer in combination.
- polyester-based segment polyglycolic acid, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-3hydroxyvalerate), polycaprolactone, or ethylene glycol
- Polyesters composed of aliphatic diols such as propanediol and butanediol and aliphatic dicarboxylic acids such as succinic acid, sebacic acid and adipic acid are preferably used as the polyester-based segment.
- the block copolymer plasticizer may contain both the polyether segment and the polyester segment in one molecule, or may be either one of the components. From the viewpoint of plasticizer productivity, cost, and the like, when using any one component, it is preferable to use a polyether-based segment from the viewpoint that desired flexibility can be imparted by adding a smaller amount of the plasticizer. That is, a preferred embodiment as a block copolymer plasticizer is a block copolymer of a polyether segment and a polylactic acid segment.
- the number average molecular weight of the polyether segment or the polyester segment in one molecule of the block copolymer plasticizer is preferably 7,000 to 20,000.
- the composition constituting the polylactic acid resin film has sufficient flexibility, and the plasticizer (C), the resin (A) (polylactic acid resin), and the resin (B).
- the melt viscosity is set to an appropriate level, and film forming processability such as an inflation film forming method can be stabilized.
- each segment block of the polyether-based and / or polyester-based segment and the polylactic acid segment is blocked from the viewpoint of more effectively suppressing bleed out. It is preferably at the end of the copolymer plasticizer molecule.
- PEG polyethylene glycol having a hydroxyl terminal at both ends
- the number average molecular weight of PEG having hydroxyl ends at both ends (hereinafter, the number average molecular weight of PEG is M PEG ) is usually calculated from the hydroxyl value determined by a neutralization method or the like in the case of a commercially available product.
- lactide w L parts by mass are added to w E parts by mass of PEG having hydroxyl groups at both ends, lactide is subjected to ring-opening addition polymerization at both hydroxyl groups of PEG and sufficiently reacted, so that PLA is substantially obtained.
- a block copolymer of the -PEG-PLA type can be obtained (where "PLA" indicates polylactic acid).
- the number average molecular weight of one polylactic acid segment of this block copolymer plasticizer can be substantially determined by (1/2) ⁇ (w L / w E ) ⁇ M PEG .
- the mass percentage of the total block copolymer plasticizer of the polylactic acid segment component can be substantially determined by 100 ⁇ w L / (w L + w E)%.
- the mass ratio of the plasticizer component excluding the polylactic acid segment component to the entire block copolymer plasticizer can be substantially calculated by 100 ⁇ w E / (w L + w E )%.
- the plasticizer (C) contained in the composition constituting the polylactic acid resin film of the present invention is preferably 5 to 30% by mass in 100% by mass of the entire composition. By setting it to 5% by mass or more, the flexibility of the film becomes high, and by setting it to 30% by mass or less, the stiffness when made into a film is strong and the handling property, strength, durability, and bleed-out resistance of the plasticizer are improved. Get higher.
- the content of the plasticizer (C) is preferably 7 to 25% by mass, more preferably 10 to 20% by mass in 100% by mass of the whole composition.
- the composition constituting the polylactic acid-based film of the present invention can contain a thermoplastic resin other than those described above for the purpose of improving various physical properties. The content is preferably 0.1 to 50% by mass, more preferably 0.3 to 40% by mass, and further preferably 0.5 to 30% by mass in 100% by mass of the entire composition.
- thermoplastic resins are polyacetal, polyethylene, polypropylene, polyamide, poly (meth) acrylate, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyether imide, ethylene / glycidyl methacrylate copolymer Polyester elastomer, polyamide elastomer, ethylene / propylene terpolymer, ethylene / butene-1 copolymer, thermoplastic starch, starch-containing polymer, and the like.
- thermoplastic resins other than polylactic acid resins examples include improving the high-temperature rigidity of polylactic acid films by containing poly (meth) acrylate, and polylactic acid films by containing polyester.
- the polymer containing starch for example, Novamont's biodegradable resin “Matterby” can be used.
- biodegradation promotion among the applications in which the polylactic acid film of the present invention is used, especially in agricultural and forestry applications such as agricultural multi-films and pine worm fumigation sheets, biodegradability promotion is required. is important.
- the resin (A) (polylactic acid resin) contained in the composition constituting the polylactic acid film of the present invention is preferably a mixture of a crystalline polylactic acid resin and an amorphous polylactic acid resin. This is because, by using a mixture, the advantages of both crystalline and amorphous polylactic acid resins can be achieved.
- the crystalline polylactic acid resin was measured with a differential scanning calorimeter (DSC) in an appropriate temperature range after the polylactic acid resin was sufficiently crystallized under heating.
- DSC differential scanning calorimeter
- it refers to a polylactic acid resin in which a melting point derived from a polylactic acid component is observed.
- the amorphous polylactic acid resin refers to a polylactic acid resin that does not exhibit a clear melting point when the same measurement is performed.
- the inclusion of the crystalline polylactic acid resin is suitable for improving the tear resistance, impact resistance, heat resistance, and blocking resistance of the film.
- the plasticizer (C) when a block copolymer plasticizer is used as the plasticizer (C), the crystalline polylactic acid-based resin forms a eutectic with the polylactic acid segment of the block copolymer plasticizer, thereby preventing bleeding out. Great effect on sex.
- an amorphous polylactic acid resin is suitable for improving the flexibility and bleed-out resistance of the film. This has an effect of providing an amorphous part in which the plasticizer can be dispersed.
- the crystalline polylactic acid-based resin used in the polylactic acid-based film of the present invention includes a content ratio of an L-lactic acid unit in poly L-lactic acid or a poly D-lactic acid from the viewpoint of improving tear resistance and impact resistance.
- the content of D-lactic acid units is preferably 96 to 100 mol%, more preferably 98 to 100 mol%, still more preferably 99 to 100 mol%, particularly preferably 99.5 out of 100 mol% of all lactic acid units. ⁇ 100 mol%.
- the amount of the resin (A) in the composition constituting the polylactic acid film of the present invention is 100% by mass (the total of the crystalline polylactic acid resin and the amorphous polylactic acid resin is 100% by mass) ),
- the ratio of the crystalline polylactic acid resin is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40%.
- the polylactic acid film of the present invention is a resin at a temperature of 200 ° C.
- the temperature 200 ° C., the viscosity ratio of the melt viscosity eta B of the resin (B) at a shear rate of 100sec -1 ( ⁇ a / ⁇ B ) is 0.2 to 2 .
- the viscosity ratio ( ⁇ A / ⁇ B ) is more preferably 0.4 to 1.5, still more preferably 0.6 to 1.1, and particularly preferably 0.6 to 1.0.
- the melt viscosity ( ⁇ A or ⁇ B ) of the resin in which the plasticizer is dispersed is changed to the plasticizer ( It is necessary to measure the melt viscosity containing C).
- the plasticizer (C) is a block copolymer having a polyether segment and a polylactic acid segment, and a block copolymer having a polyester segment and a polylactic acid segment, only the resin (A) is used. Since it disperses, ⁇ A is measured as resin (A) + plasticizer (C).
- the melt viscosity ⁇ B of the resin (B) Is preferably 400 to 1,000 Pa ⁇ s, more preferably 600 to 1,000 Pa ⁇ s. Furthermore, in this case, it is preferable to select at least one selected from the group consisting of polybutylene succinate, polybutylene succinate adipate and polybutylene adipate terephthalate as the resin B.
- polybutylene adipate terephthalate is selected as the resin (B), and that the melt viscosity of the polybutylene adipate terephthalate at a temperature of 200 ° C. and a shear rate of 100 sec ⁇ 1 is 600 to 700 Pa ⁇ s, More preferably, the melt viscosity is 630 to 670 Pa ⁇ s, and most preferably, the melt viscosity is 645 to 655 Pa ⁇ s. (Crystallization peak, calorific value)
- the polylactic acid-based film of the present invention has at least one crystallization peak in the temperature range of 105 to 160 ° C.
- the polylactic acid-based film of the present invention has at least one crystallization peak in the temperature range of 105 to 160 ° C. when cooled at a rate of 20 ° C./min from the molten state with a differential scanning calorimeter.
- the number of crystallization peaks present in the temperature range of 105 to 160 ° C. is preferably one or two.
- ⁇ Hmc A When ⁇ Hmc A is less than 0.5, the tear resistance and impact resistance are insufficient. Further, when ⁇ Hmc A exceeds 9.5, flexibility is insufficient.
- ⁇ Hmc A is preferably 0.6 ⁇ ⁇ Hmc A ⁇ 8.0, more preferably 0.7 ⁇ ⁇ Hmc A ⁇ 6.5, and 0.8 ⁇ ⁇ Hmc A ⁇ 5.0. Is more preferable, and 0.9 ⁇ ⁇ Hmc A ⁇ 3.5 is particularly preferable.
- ⁇ Hmc A is the total calorific value of the crystallization peak in the temperature range of 105 to 160 ° C. Therefore, if there is only one crystallization peak in the temperature range of 105 to 160 ° C., the calorific value of the one crystallization peak corresponds to ⁇ Hmc A. On the other hand, if there are a plurality of crystallization peaks in the temperature range of 105 to 160 ° C., the total calorific value of the plurality of crystallization peaks corresponds to ⁇ Hmc A.
- Resin (A) (polylactic acid resin) is the content of L-lactic acid units in poly L-lactic acid or D-lactic acid units in poly D-lactic acid.
- the ratio is the above-described preferable ratio, and (3) a specific crystal nucleating agent is further added.
- the method of containing by the preferable addition amount mentioned later is employable.
- crystal nucleating agent for example, the following can be used.
- organic crystal nucleating agents melamine compounds, phenylphosphonic acid metal salts, benzenecarboxamide derivatives, aliphatic / aromatic carboxylic acid hydrazides, sorbitol compounds, amino acids, polypeptides, metal phthalocyanines, and the like can be preferably used.
- melamine compounds include melamine cyanurate and melamine polyphosphate.
- phenylphosphonic phenylphosphonic acid metal salts include phenylphosphonic acid zinc salts, phenylphosphonic acid magnesium salts, and phenylphosphonic acid calcium salts.
- benzenecarboxamide derivative include N, N ′, N ′′ -tricyclohexyl-1,3,5-benzenetricarboxamide.
- silicate minerals such as talc, clay, mica and kaolinite, carbon black and the like can be preferably used.
- crystal nucleating agents are at least one selected from the group consisting of melamine compounds, phenylphosphonic acid metal salts, benzenecarboxamide derivatives, talc, clay, mica and carbon black. It is preferable in terms of improvement in impact and transparency. Furthermore, talc is particularly preferable as the crystal nucleating agent in terms of the tear resistance, impact resistance improvement ratio, and transparency, and carbon black is particularly preferable in terms of the tear resistance and impact resistance improvement ratio.
- the average particle diameter of the inorganic crystal nucleating agent excluding carbon black is preferably 0.5 to 7.5 ⁇ m, more preferably 0.8 to 5.0 ⁇ m, and 1.0 More preferably, it is ⁇ 4.0 ⁇ m.
- the average particle diameter means D50 (median diameter of particle diameter distribution) measured by a laser diffraction method.
- the average particle size of the inorganic crystal nucleating agent is preferably 10 to 75 nm, more preferably 15 to 50 nm, and even more preferably 20 to 40 nm.
- the average particle diameter of carbon black here is an arbitrary 10 particle diameters of small spherical components (having a contour due to microcrystals and cannot be separated) constituting the carbon black primary aggregate (aggregate) ( The primary particle diameter) is measured and calculated with an electron microscope at a magnification of 100,000 times, and the average of these 10 values is called the average particle diameter.
- the addition amount of the crystal nucleating agent is not particularly limited. However, in order to effectively express the nucleating agent ability, and to suppress the decrease in melt viscosity, the deterioration of workability, and the deterioration of transparency due to excessive addition, the polylactic acid type
- the total amount of the composition constituting the film is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, still more preferably 0.5 to 7.0% by mass, and 1.0% by mass. Is particularly preferably from 5.0 to 5.0% by weight, most preferably from 1.5 to 4.5% by weight.
- the polylactic acid film of the present invention preferably has an elongation in the length direction and width direction (direction perpendicular to the length direction) of 200% or more and 700% or less.
- the elongation is 200% or more, the tear resistance and impact resistance are high, and it is used for agricultural and forestry applications such as agricultural multi-films and pine worm fumigation sheets, garbage bags, compost bags, and various packaging applications. It is hard to break and improves practicality.
- the elongation is 700% or less, tarmi and wrinkles are less likely to occur during roll-to-roll running and during winding, and the roll winding shape and unwinding property are improved.
- the elongation in the length direction and the width direction is more preferably from 250% to 600%, and even more preferably from 300% to 500%.
- the polylactic acid-based film of the present invention has an average value E L of elongation (%) in the length direction and the width direction (direction perpendicular to the length direction) at 5 ° C., and the length direction and width at 23 ° C.
- mean value E H in the direction of elongation (%) is preferably the following conditions are met.
- E L / E H ⁇ 0.70 Agricultural and forestry applications such as agricultural multi-film and pine worm fumigation sheets, garbage bags and compost bags, food bags such as vegetables and fruits, various packaging applications such as bags for various industrial products, etc. Work may be performed under low temperature conditions. In general, plastic films tend to decrease in elongation at lower temperatures, and as a result, when working under low-temperature conditions, the film is easily torn or torn and the workability is significantly reduced. To do. Therefore, when the elongation of the film satisfies the above conditions, the workability can be minimized.
- the relationship between E L and E H is more preferably E L / E H ⁇ 0.75, and more preferably E L / E H ⁇ 0.80.
- the upper limit of E L / E H is 1.00.
- Examples of a method for adjusting the elongation in the length direction and the width direction to 200 to 700% include polylactic acid resins, aliphatic polyester resins other than polylactic acid resins, and / or aliphatic aromatic polyester resins. And a method of setting the blending amount of the plasticizer within the above-described preferred ranges.
- E L and E H are, as a method for satisfying the E L / E H ⁇ 0.70, is not particularly limited, for example, in addition to methods of accomplishing the elongation of the (crystallization peak calorific value)
- the method of adding the crystal nucleating agent described in the item in the above-mentioned preferable amount can be mentioned.
- the polylactic acid film of the present invention preferably has a tensile modulus of 100 to 1,500 MPa in the length direction and the width direction in order to impart sufficient flexibility.
- the tensile modulus is more preferably 200 to 1,200 MPa, and further preferably 300 to 1,000 MPa.
- Examples of a method for setting the tensile modulus in the length direction and the width direction to 100 to 1,500 MPa include polylactic acid resins, aliphatic polyester resins other than polylactic acid resins, and / or aliphatic aromatic polyester systems.
- the method of making the compounding quantity of resin and a plasticizer into the preferable range mentioned above, respectively is mentioned.
- the polylactic acid film of the present invention preferably has a film thickness of 5 to 200 ⁇ m. By setting the film thickness to 5 ⁇ m or more, the firmness of the film becomes strong, the handleability is excellent, and the roll winding shape and unwinding property are good.
- the film thickness is more preferably 7 to 150 ⁇ m, further preferably 10 to 100 ⁇ m, and still more preferably 12 to 50 ⁇ m.
- Heat shrinkage When the polylactic acid film of the present invention is treated at 65 ° C. for 30 minutes, the thermal shrinkage in the length direction and the width direction is preferably ⁇ 5 to 5%.
- the composition constituting the polylactic acid film of the present invention preferably contains 0.1 to 5% by mass of organic lubricant in 100% by mass of the whole composition.
- 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 , Fatty acid (partial) esters of polyhydric alcohols such as glycerin fatty acid esters and rubitan fatty acid esters, long chain fatty acid esters such as long chain ester waxes such as butyl stearate and montan wax And the like.
- liquid paraffins such as polyethylene, stearic acid, la
- fatty acid amide organic lubricants that are easy to obtain an effect in a small amount due to moderate compatibility with polylactic acid are preferred.
- organic lubricants having a relatively high melting point such as ethylene bis stearic acid amide, ethylene bis oleic acid amide, and ethylene bis lauric acid amide are preferable from the viewpoint of expressing better blocking resistance.
- the polylactic acid-based film of the present invention preferably has a haze of 50% or less, and more preferably 40% or less. When the haze is 50% 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.
- composition which comprises the polylactic acid-type film of this invention you may contain additives other than having mentioned above in the range which does not impair the effect of this invention.
- additives for example, known antioxidants, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, antioxidants, ion exchange agents, tackifiers, antifoaming agents Agents, coloring pigments, dyes and the like.
- antioxidants 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.
- Particles may be added to the composition constituting the polylactic acid film of the present invention for the purpose of improving the slipperiness and blocking resistance of the processed product.
- inorganic 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, wollastonite, potassium titanate, aluminum boride, and zepiolite.
- various composite oxides such as, various phosphates such as lithium phosphate, calcium phosphate and magnesium phosphate, various oxides such as aluminum oxide, titanium oxide, zirconium oxide and zinc oxide, water such as aluminum hydroxide and magnesium hydroxide Fine particles made of various salts such as oxide and lithium fluoride can be used.
- These inorganic particles are surface-treated with fatty acids, resin acids, titanate coupling agents, silane coupling agents, phosphate esters, etc. for the purpose of increasing compatibility with the resin and preventing aggregation in the resin. May be applied.
- organic particles fine particles made of calcium oxalate, terephthalate such as calcium, barium, zinc, manganese, magnesium, etc. are used.
- 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 average particle size of both inorganic particles and organic particles is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 4 ⁇ m, and most preferably 0.5 to 3 ⁇ m.
- the carboxyl group terminal concentration of the film is preferably 30 equivalents / 10 3 kg or less, more preferably 20 equivalents / 10 3 kg or less, and even more preferably 10 equivalents. / 10 3 kg or less.
- the carboxyl group terminal concentration of the film is 30 equivalents / 10 3 kg or less, the carboxyl group terminal concentration that also serves as a hydrolysis autocatalyst is sufficiently low. There are many cases where this is possible.
- Examples of the method for adjusting the carboxyl group terminal concentration of the film to 30 equivalents / 10 3 kg or less include, for example, a method of controlling by a catalyst and a heat history at the time of synthesizing a polylactic acid resin, lowering an extrusion temperature at the time of film formation or Examples thereof include a method of reducing the heat history such as shortening the residence time, a method of blocking the 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 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 which is the resin (A) in the present invention can be obtained, for example, by the following method.
- a lactic acid component of L-lactic acid or D-lactic acid is mainly used, 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 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.
- composition constituting the polylactic acid film of the present invention that is, resin (A) (polylactic acid resin), resin (B) (aliphatic polyester resin other than polylactic acid resin and / or aliphatic aromatic polyester) System resin), a plasticizer (C), or a composition containing other components such as a crystal nucleating agent, a solution in which each component is dissolved in a solvent is uniformly mixed, and then the solvent is removed.
- resin (A) polylactic acid resin
- resin (B) aliphatic polyester resin other than polylactic acid resin and / or aliphatic aromatic polyester) System resin
- a plasticizer (C) or a composition containing other components such as a crystal nucleating agent, a solution in which each component is dissolved in a solvent is uniformly mixed, and then the solvent is removed.
- a melt-kneading method for producing a composition by melt-kneading each component. It is preferable to adopt.
- 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 190 ° C. to 210 ° C. from the viewpoint of preventing deterioration of the polylactic acid resin.
- the polylactic acid-based film of the present invention can be obtained by, for example, 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 pellet is heated at 60 to 100 ° C. It is preferable to use a composition containing a polylactic acid resin or the like having a moisture content of 1,200 ppm or less, preferably 500 ppm or less, more preferably 200 ppm or less by drying for 6 hours or more. Furthermore, it is preferable to reduce the lactide content in the composition containing a polylactic acid resin or the like by vacuum drying under a high vacuum with a degree of vacuum of 10 Torr or less.
- the melt viscosity at the time of preparing a composition containing a resin or the like can be set to an appropriate level and the film forming process can be stabilized. From the same point of view, when pelletizing or melt-extrusion / film formation, a twin-screw extruder with a vent hole is used and melt extrusion is performed while removing volatiles such as moisture and low molecular weight substances. It is preferable.
- the composition prepared by the above-described method is melt-extruded by a twin-screw extruder with a vent hole, led to an annular die, and extruded from the annular die. Then, dry air is supplied inside and formed into a balloon shape (bubble), further air-cooled and solidified uniformly by an air ring, and taken up at a predetermined take-up speed while being folded flat with a nip roll, then both ends as necessary. Alternatively, one end may be cut open and wound. Then, in order to suppress the heat shrink of a film, you may heat-process in a heating roll or oven.
- the thickness may be adjusted to 5 to 200 ⁇ m depending on the discharge amount from the annular die, the take-up speed of the nip roll, and the bubble blowing ratio.
- the annular die is spiral. It is preferable to use a mold, and from the same viewpoint, it is preferable to use a rotary die.
- the extrusion temperature of the composition constituting the polylactic acid-based film of the present invention is usually in the range of 150 to 240 ° C., but in order to promote effective crystallization in order to develop good tear resistance and impact resistance.
- the temperature of the annular die is important, and the temperature of the annular die is in the range of 150 to 190 ° C, preferably 155 to 185 ° 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 film of the present invention is excellent in bleed resistance and blocking resistance, it can be smoothly unwound without problems when the film is unwound from the film roll after being wound.
- the crystallization peak temperature and calorific value are It was determined according to the method specified in K 7121 (1987).
- ⁇ Hmc A was determined by adding the calorific value of the crystallization peak existing in the region from 105 ° C. to 160 ° C.
- E L of elongation (%) in the length direction and width direction at 5 ° C. and average value E H of elongation (%) in the length direction and width direction at 23 ° C.
- Stress-strain measurement was performed at 5 ° C. and 23 ° C. using TENSILON UCT-100 manufactured by Orientec Co., Ltd. equipped with a thermostatic bath.
- a sample was cut into a strip shape having a length of 150 mm and a width of 10 mm in the measurement direction, and in a constant temperature bath adjusted to 5 ° C., the initial tensile chuck distance was 50 mm, the tensile speed was 200 mm / min, and JIS Measured according to the method specified in K 7127 (1999), the average elongation (%) of 10 measurements was obtained in the length direction and the width direction, respectively, E LMD and E LTD , respectively. EL was calculated.
- E L (E LMD + E LTD ) / 2
- E HMD E HTD
- the sample size was 63 mm in the tear direction ⁇ 76 mm in the direction perpendicular to the tear, and 20 mm incision was made in the tear direction, and the indicated value when the remaining 43 mm was torn was read.
- (5) Impact strength (kN ⁇ m / mm) Using a film impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), impact strength was measured in an atmosphere of a temperature of 23 ° C. and a humidity of 65% RH using a hemispherical impact head having a diameter of 1/2 inch. The measurement was performed 10 times per level, and was obtained from the average value of 10 measurements.
- the pellets of this composition were vacuum-dried at a temperature of 60 ° C. for 12 hours using a rotary drum type vacuum dryer.
- the polylactic acid-based film of the present invention is excellent in flexibility, tear resistance, impact resistance, and excellent in blocking resistance and bleed-out resistance. It is a film, and is preferably used for agricultural and forestry applications such as agricultural multi-film and pine worm fumigation sheets, garbage bags and compost bags, food bags such as vegetables and fruits, and various packaging applications such as bags for various industrial products. be able to.
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Abstract
Description
本発明のポリ乳酸系フィルムは、可塑剤(C)が、ポリエーテル系セグメントとポリ乳酸セグメントとを有するブロック共重合体、および/または、ポリエステル系セグメントとポリ乳酸セグメントとを有するブロック共重合体であることが好ましい。
本発明のポリ乳酸系フィルムは、メラミン系化合物、フェニルホスホン酸金属塩、ベンゼンカルボアミド誘導体、タルク、クレー、マイカおよびカーボンブラックからなる群より選ばれる少なくとも1つを、前記組成物の全量100質量%中、0.1~20質量%含有することが好ましい。
以下、本発明のポリ乳酸系フィルムについて説明する。
(樹脂(A)(ポリ乳酸系樹脂))
本発明のポリ乳酸系フィルムは、樹脂(A)を含む組成物からなることが重要である。ここで樹脂(A)とは、ポリ乳酸系樹脂を意味する。またポリ乳酸系樹脂とは、L-乳酸ユニットおよび/またはD-乳酸ユニットを主たる構成成分とする重合体である。ここで主たる構成成分とは、重合体中の単量体ユニット全体100mol%中において乳酸ユニットの割合が最大であることを意味し、好ましくは全単量体ユニット100mol%中、乳酸ユニットが70~100mol%である。
(樹脂(B)(ポリ乳酸系樹脂以外の脂肪族ポリエステル系樹脂および/または脂肪族芳香族ポリエステル系樹脂))
本発明のポリ乳酸系フィルムは、柔軟性、耐引き裂き性、耐衝撃性を発現させるために、樹脂(B)を含む組成物からなることが重要である。ここで樹脂(B)とは、ポリ乳酸系樹脂以外の脂肪族ポリエステル系樹脂および/または脂肪族芳香族ポリエステル系樹脂である。また、フィルムの生分解性発現のため、樹脂(B)も生分解性を有することが好ましい。これらの樹脂は、生分解速度の調整、およびポリ乳酸系フィルムを構成する組成物全体の溶融粘度を調整して特にインフレーション製膜法において安定したバブルを形成する役割も果たす。
(可塑剤(C))
本発明のポリ乳酸系フィルムは、主に柔軟性を付与するために可塑剤(C)を含む組成物からなることが重要である。
(その他の樹脂)
本発明のポリ乳酸系フィルムを構成する組成物には、様々な物性改良を目的に、上記以外の熱可塑性樹脂を含有することができる。含有量は、該組成物全体100質量%中、0.1~50質量%が好ましく、0.3~40質量%がより好ましく、0.5~30質量%がさらに好ましい。
(結晶性ポリ乳酸系樹脂と非晶性ポリ乳酸系樹脂の混合)
本発明のポリ乳酸系フィルムを構成する組成物に含有される樹脂(A)(ポリ乳酸系樹脂)は、結晶性ポリ乳酸系樹脂と非晶性ポリ乳酸系樹脂の混合物であることが好ましい。混合物とすることにより、結晶性、非晶性、それぞれのポリ乳酸系樹脂の利点を両立できるからである。
(樹脂(A)と樹脂(B)の溶融粘度の関係)
本発明のポリ乳酸系フィルムは、フィルムの耐引き裂き性、耐衝撃性、伸度、透明性を向上させ、熱収縮率を抑制するためには、温度200℃、剪断速度100sec-1における樹脂(A)の溶融粘度ηAと、温度200℃、剪断速度100sec-1における樹脂(B)の溶融粘度ηBとの粘度比(ηA/ηB)が0.2~2であることが好ましい。粘度比(ηA/ηB)は0.4~1.5がより好ましく、0.6~1.1がさらに好ましく、0.6~1.0が特に好ましい。
(結晶化ピーク、発熱量)
本発明のポリ乳酸系フィルムは、示差走査型熱量計にて融解状態から20℃/minの速度で冷却した際に105~160℃の温度領域に少なくともひとつの結晶化ピークを有し、105~160℃の温度領域の結晶化ピークの発熱量の合計をΔHmcAとしたとき、次の条件を満たすことが重要である。
発明者らは、これらの結晶化ピーク温度と発熱量の条件を有することで、ポリ乳酸系フィルムに柔軟性と、耐引き裂き性、耐衝撃性を付与せしめることが可能であることを見出した。これは、上記条件を満たす場合、ポリ乳酸系フィルムを溶融押し出し製膜する際、特にインフレーション法で製膜する際に、口金から空気中に押し出された樹脂が、耐引き裂き性、耐衝撃性の発現に有効な結晶化を進めるためである。本発明のポリ乳酸系フィルムの製造方法は後述する。
(伸度)
本発明のポリ乳酸系フィルムは、長さ方向および幅方向(長さ方向と垂直な方向)の伸度が、いずれも200%以上700%以下であることが好ましい。伸度が200%以上であると耐引き裂き性、耐衝撃性が高くなり、農業用マルチフィルムや松くい虫燻蒸用シートなどの農林業用途やゴミ袋、堆肥袋、あるいは各種包装用用途とした際に破れにくく実用性が向上する。また、伸度が700%以下であると製膜時にロール間走行時や巻き取り時のタルミやシワが生じにくく、ロール巻姿や巻出し性が良好となる。長さ方向および幅方向の伸度は、250%以上600%以下がより好ましく、300%以上500%以下がさらに好ましい。
農業用マルチフィルムや松くい虫燻蒸用シートなどの農林業用途、ゴミ袋や堆肥袋、あるいは野菜や果物など食料品用袋、各種工業製品の袋など各種包装用途などに用いる際に、比較的低温条件下で作業を行う場合がある。一般的にプラスチックフィルムは温度が低くなると伸度が低下する傾向があり、その結果、低温条件下での作業時に、フィルムが破れやすくなったり、引き裂かれやすくなったりして、作業性が著しく低下する。そこで、フィルムの伸度が上記条件を満たすことで、該作業性の低下を最小限に抑えることができる。ELとEHの関係は、EL/EH≧0.75であることがより好ましく、EL/EH≧0.80であることがさらに好ましい。なお、EL/EHの上限値は、1.00である。
(弾性率)
本発明のポリ乳酸系フィルムは、十分な柔軟性を付与するために、長さ方向、幅方向それぞれの引張弾性率が100~1,500MPaであることが好ましい。引張弾性率は、200~1,200MPaであることがより好ましく、300~1,000MPaであることがさらに好ましい。
(厚み)
本発明のポリ乳酸系フィルムは、フィルム厚みが5~200μmであることが好ましい。フィルム厚みを5μm以上とすることで、フィルムとした際のコシが強くなり、取り扱い性に優れ、また、ロール巻姿や巻出し性が良好となる。フィルム厚みを200μm以下とすることで柔軟性が向上し、農業用マルチフィルムや松くい虫燻蒸用シートなどの農林業用途やゴミ袋、堆肥袋、あるいは各種包装用用途とした際に取り扱い性に優れるものとなり、また、特にインフレーション製膜法においては、自重によりバブルが不安定化しない。フィルム厚みは、7~150μmがより好ましく、10~100μmがさらに好ましく、12~50μmがさらにより好ましい。
(熱収縮率)
本発明のポリ乳酸系フィルムは、65℃、30分間で処理した時の、長さ方向と幅方向の熱収縮率は、-5~5%であることが好ましい。5%以下とすることで、巻き取った後のフィルムの経時収縮、いわゆる巻締りによる巻姿の悪化を抑制できる。さらには巻き硬度が高くなりすぎることによるブロッキングの発生を抑制できる。また、-5%以上とすることで、巻き取った後のフィルムが経時で長さ方向に弛むことによる、巻姿の悪化を抑制できる。なおここで、熱収縮率が0未満のマイナスの値をとる場合は、フィルムが伸長することを意味する。
(有機滑剤)
本発明のポリ乳酸系フィルムを構成する組成物は、組成物全体100質量%中、有機滑剤を0.1~5質量%含むことが好ましい。この場合、巻き取り後のブロッキングを良好に抑制できる。また、有機滑剤の添加過多による溶融粘度の低下や加工性の悪化、あるいはフィルムとした際のブリードアウトやヘイズアップなどの外観不良の問題も発生しにくい。
(ヘイズ)
本発明のポリ乳酸系フィルムは、ヘイズが50%以下であることが好ましく、40%以下であることがさらに好ましい。ヘイズが50%以下である場合、野菜や果物など食料品用袋、各種工業製品の袋など各種包装用途などに成形加工した際には内容物が容易に確認できる、商品としての見栄えがよいなど高い意匠性により好適である場合が多い。なお、ポリ乳酸の一般的な特性から、ポリ乳酸系フィルムのヘイズとしては1%未満にすることは困難であることから、下限は1%程度である。
(添加剤)
本発明のポリ乳酸系フィルムを構成する組成物には、本発明の効果を損なわない範囲で前述した以外の添加剤を含有してもよい。例えば、公知の酸化防止剤、紫外線安定化剤、着色防止剤、艶消し剤、消臭剤、難燃剤、耐候剤、帯電防止剤、抗酸化剤、イオン交換剤、粘着性付与剤、消泡剤、着色顔料、染料などが含有できる。
(粒子)
本発明のポリ乳酸系フィルムを構成する組成物には、加工品の易滑性や耐ブロッキング性の向上などを目的として、粒子を添加してもよい。
例えば無機粒子としては、シリカ等の酸化ケイ素、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等の各種炭酸塩、硫酸カルシウム、硫酸バリウム等の各種硫酸塩、ウォラストナイト、チタン酸カリウム、ホウ化アルミニウム、ゼピオライト等の各種複合酸化物、リン酸リチウム、リン酸カルシウム、リン酸マグネシウム等の各種リン酸塩、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化亜鉛等の各種酸化物、水酸化アルミニウム、水酸化マグネシウム等の水酸化物、フッ化リチウム等の各種塩等からなる微粒子を使用することができる。
(カルボキシル基末端)
本発明のポリ乳酸系フィルムは、特に各種工業製品の包装用途など生分解性を必要としない場合や保管耐久性があった方が好ましい用途においては、ポリ乳酸系樹脂の加水分解による強度低下を抑制し、良好な耐久性を付与する観点から、該フィルムのカルボキシル基末端濃度が30当量/103kg以下であることが好ましく、より好ましくは20当量/103kg以下、さらに好ましくは10当量/103kg以下である。該フィルムのカルボキシル基末端濃度が30当量/103kg以下であると、加水分解の自己触媒ともなるカルボキシ基末端濃度が十分低いために、用途にもよるが実用的に良好な耐久性を付与できる場合が多い。
(製造方法)
次に、本発明のポリ乳酸系フィルムを製造する方法について具体的に説明するがこれに限定されるものではない。
[測定および評価方法]
実施例中に示す測定や評価は次に示すとおりの条件で行った。
(1)結晶化ピーク温度(℃)、発熱量ΔHmcA(J/g)
セイコーインスツル(株)製示差走査熱量計RDC220を用い、フィルム試料5mgをアルミニウム製受皿にセットし、25℃から昇温速度20℃/分で250℃まで昇温、250℃のまま5分間溶融保持したのち、降温速度20℃/分で25℃まで降温した。その降温時に観測される結晶化ピークをもとに、結晶化ピーク温度、発熱量を、JIS
K 7121(1987)に規定された方法に従って求めた。なおΔHmcAは、105℃から160℃の領域に存在する結晶化ピークの発熱量を合計することで求めた。
(2)5℃における長さ方向と幅方向の伸度(%)の平均値ELと、23℃における長さ方向と幅方向の伸度(%)の平均値EH
恒温槽を備えた(株)オリエンテック製TENSILON UCT-100を用いて、5℃、23℃それぞれにおける応力-歪み測定を行った。
K 7127(1999)に規定された方法に従って測定を行い、10回の測定の平均伸度(%)を、長さ方向と幅方向について求め、それぞれ、ELMD、ELTDとし、下記式にてELを算出した。
同様にして、23℃に調整された恒温槽の中で測定を行い、10回の測定の平均伸度(%)を、長さ方向と幅方向について求め、それぞれ、EHMD、EHTDとし、下記式にてEHを算出した。
(3)引張弾性率(MPa)
(2)に記載した方法で、23℃における応力-歪み測定を行い、応力-歪み曲線の最初の直線部分を用いて、直線上の2点間の応力の差を同じ2点間の歪みの差で除し、引張弾性率を計算した。測定は計10回行い、その平均値を採用した。これを長さ方向、幅方向、それぞれについて算出した。
(4)引き裂き強度(N/mm)
(株)東洋精機製作所製引き裂き伝播抵抗計(エレメンドルフ)を用いて、JIS K 7128-2に規定された方法に従って測定した。サンプルサイズは引き裂き方向63mm×引き裂きと垂直方向76mmで、引き裂き方向に20mmの切れ込みを入れ、残り43mmを引き裂いた時の指示値を読みとった。
(5)インパクト強度(kN・m/mm)
フィルムインパクトテスター((株)東洋精機製作所製)により、直径1/2inchの半球状衝撃頭を用い、温度23℃、湿度65%RHの雰囲気下においてインパクト強度の測定を行った。測定は1水準につき10回行い、10回の測定の平均値から求めた。さらに、フィルムサンプルの平均厚さ(mm)で割り返し、単位厚み当たりの値として求めた。
(6)ヘイズ(%)
ヘイズメーターHGM-2DP型(スガ試験機(株)製)を用いてJIS K 7136(2000)に規定された方法に従ってヘイズ値を測定した。測定は1水準につき5回行い、5回の測定の平均値から求めた。
(7)巻き出し性
ロールサンプルを温度23℃、湿度65%RHの雰囲気下において3日間保管の後、ロールサンプルの紙管に紙管の内径より小さい直径の鉄製軸を通し、鉄製軸の両端をフックにかけてロールを水平に、且つ自由に回転できる状態で掛けおいた状態とし、フィルムを10m/minの速度で巻き出した際の巻出しの様子を目視にて観察し、次の基準にて判断した。
A:問題なく滑らかに巻き出すことができる。
C:時々不連続な巻出しとなる。
F:断続的に不連続な巻出しとなる。
(8)溶融粘度
(株)島津製作所製フローテスターCFT-500A(ダイ径1mm、ダイ長10mm、プランジャ断面積1cm2)を用いて、温度200℃、予熱3分で測定、剪断速度100sec-1の溶融粘度の値(Pa・s)を用いた。
[樹脂(A)]
(A1)
ポリL-乳酸、質量平均分子量200,000、D体含有量1.4%、融点166℃、温度200℃、剪断速度100sec-1における溶融粘度1,400Pa・s
(A2)
ポリL-乳酸、質量平均分子量200,000、D体含有量5.0%、融点150℃、温度200℃、剪断速度100sec-1における溶融粘度1,400Pa・s
(A3)
ポリL-乳酸、質量平均分子量200,000、D体含有量12.0%、融点無し、温度200℃、剪断速度100sec-1における溶融粘度1,400Pa・s
(A4)
ポリD-乳酸、質量平均分子量20,000、L体含有量1.5%
(A5)
ポリL-乳酸、質量平均分子量200,000、D体含有量0.5%、融点180℃、温度200℃、剪断速度100sec-1における溶融粘度1,400Pa・s
なお、上記の質量平均分子量は日本ウォーターズ(株)製、Waters2690を用い、ポリメチルメタクリレートを標準とし、カラム温度40℃、クロロホルム溶媒を用いて測定した。
[樹脂(B)]
(B1)
ポリブチレンアジペート・テレフタレート樹脂(BASF社製、商品名“エコフレックス”FBX7011)、温度200℃、剪断速度100sec-1における溶融粘度1,200Pa・s
(B2)
ポリブチレンサクシネート系樹脂(三菱化学(株)製、商品名“GSPla”(登録商標)AZ91T)、温度200℃、剪断速度100sec-1における溶融粘度1,050Pa・s
(B3)
ポリブチレンサクシネート・アジペート系樹脂(昭和高分子(株)製、商品名“ビオノーレ”(登録商標)#3001)、温度200℃、剪断速度100sec-1における溶融粘度1,250Pa・s
(B4)
ポリブチレンアジペート・テレフタレート樹脂(BASF社製、商品名“エコフレックス”FBX7020)、温度200℃、剪断速度100sec-1における溶融粘度650Pa・s
(B5)
ポリブチレンサクシネート系樹脂(三菱化学(株)製、商品名“GSPla” (登録商標)AZ81T)、温度200℃、剪断速度100sec-1における溶融粘度900Pa・s
(B6)
ポリブチレンサクシネート・アジペート系樹脂(昭和高分子(株)製、商品名“ビオノーレ”(登録商標)#3010)、温度200℃、剪断速度100sec-1における溶融粘度750Pa・s
[可塑剤(C)]
(C1)
数平均分子量8,000のポリエチレングリコール62質量部とL-ラクチド38質量部とオクチル酸スズ0.05質量部を混合し、撹拌装置付きの反応容器中で、窒素雰囲気下160℃で3時間重合することで、数平均分子量8,000のポリエチレングリコールの両末端に数平均分子量2,500のポリ乳酸セグメントを有する可塑剤C1を得た。
(C2)
アセチルトリブチルクエン酸(ATBC)、森村商事(株)製、商品名“シトロフレックス(登録商標)A-4”)
[有機滑剤]
(滑剤1)
エチレンビスステアリン酸アミド(日本化成(株)製、商品名“スリパックスE”(登録商標))
(滑剤2)
ステアリン酸アミド(日油(株)製、商品名“アルフロー(登録商標)S-10”)
[結晶核剤]
(核剤1)
タルク(日本タルク(株)製、商品名“SG-95”、平均粒子径2.5μm)
(核剤2)
カーボンブラック(三菱化学(株)製、商品名“RCF#45”、平均粒子経24nm)
(核剤3)
フェニルホスホン酸亜鉛塩(日産化学工業(株)製、商品名“PPA-Zn”)
[その他]
(炭酸カルシウム)
炭酸カルシウム(丸尾カルシウム(株)製、商品名“カルテックスR”、平均粒子径2.8μm)
[ポリ乳酸系フィルムの作製]
(実施例1)
ポリ乳酸(A1)55質量部、可塑剤(C1)16質量部、有機滑剤(滑剤1)1質量部、結晶核剤(核剤1)3質量部の混合物をシリンダー温度190℃のスクリュー径44mmの真空ベント付き2軸押出機に供し、真空ベント部を脱気しながら溶融混練し、均質化した後にペレット化して組成物を得た。
Claims (9)
- 樹脂(A)、樹脂(B)、可塑剤(C)を含む組成物からなるポリ乳酸系フィルムであって、樹脂(A)がポリ乳酸系樹脂、樹脂(B)がポリ乳酸系樹脂以外の脂肪族ポリエステル系樹脂および/または脂肪族芳香族ポリエステル系樹脂であり、示差走査型熱量計にて融解状態から20℃/minの速度で冷却した際に105~160℃の温度領域に少なくともひとつの結晶化ピークを有し、105~160℃の温度領域の結晶化ピークの発熱量の合計をΔHmcAとしたとき、次の条件を満たすポリ乳酸系フィルム。
0.5≦ΔHmcA≦9.5 - 可塑剤(C)が、ポリエーテル系セグメントとポリ乳酸セグメントとを有するブロック共重合体、および/または、ポリエステル系セグメントとポリ乳酸セグメントとを有するブロック共重合体である請求項1に記載のポリ乳酸系フィルム。
- 樹脂(B)が、ポリブチレンサクシネート、ポリブチレンサクシネート・アジペートおよびポリブチレンアジペート・テレフタレートからなる群より選ばれる少なくとも1つである請求項1または2に記載のポリ乳酸系フィルム。
- 樹脂(B)の温度200℃、剪断速度100sec-1における溶融粘度が400~1,000Pa・sである請求項1~3のいずれかに記載のポリ乳酸系フィルム。
- 樹脂(B)がポリブチレンアジペート・テレフタレートであり、該ポリブチレンアジペート・テレフタレートの温度200℃、剪断速度100sec-1における溶融粘度が600~700Pa・sである請求項1~4のいずれかに記載のポリ乳酸系フィルム。
- 5℃における長さ方向と幅方向(長さ方向と垂直な方向)の伸度(%)の平均値ELと、23℃における長さ方向と幅方向の伸度(%)の平均値EHが、次の条件を満たす請求項1~5のいずれかに記載のポリ乳酸系フィルム。
EL/EH≧0.70 - メラミン系化合物、フェニルホスホン酸金属塩、ベンゼンカルボアミド誘導体、タルク、クレー、マイカおよびカーボンブラックからなる群より選ばれる少なくとも1つを、前記組成物の全量100質量%中、0.1~20質量%含有する請求項1~6のいずれかに記載のポリ乳酸系フィルム。
- 樹脂(A)が、結晶性ポリ乳酸系樹脂と非晶性ポリ乳酸系樹脂の混合物である請求項1~7のいずれかに記載のポリ乳酸系フィルム。
- 長さ方向、幅方向それぞれの引張弾性率が100~1,500MPaである請求項1~8のいずれかに記載のポリ乳酸系フィルム。
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Cited By (10)
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JP2013155224A (ja) * | 2012-01-27 | 2013-08-15 | Toray Ind Inc | 生分解性フィルム |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013155224A (ja) * | 2012-01-27 | 2013-08-15 | Toray Ind Inc | 生分解性フィルム |
JP2013159747A (ja) * | 2012-02-08 | 2013-08-19 | Toray Ind Inc | ポリ乳酸系フィルム |
JP2013216743A (ja) * | 2012-04-05 | 2013-10-24 | Lonseal Corp | 耐熱性ポリ乳酸系成形体、およびその製造方法 |
JPWO2014054278A1 (ja) * | 2012-10-05 | 2016-08-25 | 株式会社カネカ | ポリエステル樹脂組成物およびその製造方法 |
JP2014083687A (ja) * | 2012-10-19 | 2014-05-12 | Toray Ind Inc | フィルム |
WO2014069379A1 (en) * | 2012-11-01 | 2014-05-08 | Toray Industries,Inc. | Multi-layered film |
CN104936779A (zh) * | 2012-11-01 | 2015-09-23 | 东丽株式会社 | 多层膜 |
EP2914432A4 (en) * | 2012-11-01 | 2016-07-13 | Toray Industries | MULTILAYER MOVIE |
JP2014122273A (ja) * | 2012-12-21 | 2014-07-03 | Toray Ind Inc | 多重フィルムおよびそれからなる農業用フィルム |
JP2017505837A (ja) * | 2014-01-31 | 2017-02-23 | バイオ−テック ビオローギッシュ ナチューフェアパックンゲン ゲーエムベーハー ウント コンパニ カーゲー | Pllaおよびpdlaを含むポリマー組成物 |
JP2015193750A (ja) * | 2014-03-31 | 2015-11-05 | 大阪瓦斯株式会社 | 生分解性樹脂組成物 |
JP7437737B2 (ja) | 2019-01-24 | 2024-02-26 | ユニチカ株式会社 | 樹脂組成物およびそれを成形して得られる管状成形体 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2011162046A1 (ja) | 2013-08-19 |
CN102892817A (zh) | 2013-01-23 |
CN102892817B (zh) | 2016-12-28 |
EP2583994A1 (en) | 2013-04-24 |
EP2583994A4 (en) | 2014-08-13 |
KR20130089159A (ko) | 2013-08-09 |
JP5867084B2 (ja) | 2016-02-24 |
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