WO2010103915A1 - ポリ乳酸系積層シート - Google Patents
ポリ乳酸系積層シート Download PDFInfo
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- WO2010103915A1 WO2010103915A1 PCT/JP2010/052708 JP2010052708W WO2010103915A1 WO 2010103915 A1 WO2010103915 A1 WO 2010103915A1 JP 2010052708 W JP2010052708 W JP 2010052708W WO 2010103915 A1 WO2010103915 A1 WO 2010103915A1
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- layer
- mass
- polylactic acid
- laminated sheet
- sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2425/00—Cards, e.g. identity cards, credit cards
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
Definitions
- the present invention relates to a polylactic acid-based laminated sheet which is excellent in impact resistance, blocking resistance and ruled line workability, and is particularly suitable for molded products and printing applications.
- Patent Document 1 discloses a system in which a biodegradable aliphatic polyester having a glass transition point Tg of 0 ° C. or less is contained in a polylactic acid resin.
- Patent Documents 2 and 3 disclose laminated films.
- Patent Document 4 discloses a laminated sheet or film. JP-A-9-111107 Japanese Patent Laid-Open No. 2004-2776 JP 2003-170560 A JP 2006-305992 A
- Patent Document 1 discloses a system in which a polylactic acid resin contains a biodegradable aliphatic polyester having a glass transition point Tg of 0 ° C. or less. There is a problem that sufficient transparency cannot be ensured because it is simply formulated.
- Patent Documents 2 and 3 disclose laminated films. However, since they all relate to stretched films, there is a problem that they are not suitable for use in forming a three-dimensional shape.
- Patent Document 4 discloses a laminated film, but since the intermediate layer of the three-layer laminated structure is 100% polylactic acid, it did not have sufficient characteristics in terms of impact resistance.
- the present invention is intended to provide a polylactic acid-based laminated sheet that is excellent in impact resistance, blocking resistance, and ruled line workability, and is particularly suitable for printing applications. Furthermore, in addition to the above-described problems, the present invention also provides a laminated sheet imparted with transparency and whiteness.
- the present invention employs the following means in order to solve the above problems.
- It is a laminated sheet comprising at least three layers, having layer A as at least one outermost layer and layer B as an inner layer, Layer A contains polylactic acid and a polybutylene succinate-based resin. Further, in 100% by mass of all components of layer A, polylactic acid is 60% by mass or more and 97.5% by mass or less (hereinafter referred to as all of layer A).
- the mass ratio of polylactic acid in 100% by mass of the component is referred to as Pa), and the ratio Xa of the thickness of the layer A is 10 to 40% with respect to 100% of the total thickness of the laminated sheet,
- Layer B contains polylactic acid and a polybutylene succinate-based resin, and the polylactic acid is 90% by mass or more and less than 100% by mass in 100% by mass of all the components of layer B (hereinafter, all components 100 of layer B are 100% by mass).
- the mass proportion of polylactic acid in mass% is referred to as Pb), A laminated sheet having a plane orientation degree ⁇ P of 0 or more and 0.002 or less.
- a polylactic acid-based laminated sheet that is excellent in impact resistance, blocking resistance, and ruled line workability, and is particularly suitable for printing applications. Furthermore, according to the preferable aspect of this invention, it is also possible to provide transparency or whiteness according to the use. By using the laminated sheet of the present invention, it is possible to obtain a molded product having a low environmental load without impairing the impact resistance, molding processability and printing processability of the conventional petroleum resin sheet.
- the term “sheet” is used to mean a two-dimensional structure such as a film or a plate
- the “molded product” is hereinafter referred to as a three-dimensional structure such as a container or It is used to mean a printed material or a card or the like that includes a processed sheet.
- the laminated sheet of the present invention is a laminated sheet composed of at least three layers having the layer A as at least one outermost layer and the layer B as an inner layer.
- the layer A may be provided on both sides of the outermost layer of the laminated sheet or may be provided on one side, but the most preferable form is a form in which both outermost layers become the layer A.
- the layer B is not particularly limited as long as it is an inner layer.
- the layer B is arranged at the center if it has a three-layer structure, and is arranged at any position other than the outermost layer if it has a five-layer structure.
- the number of laminated sheets is not particularly limited as long as it has layer A as at least one outermost layer and layer B as an inner layer, but is preferably 3 or more and 8 or less, more preferably 3 or more.
- the number of the layers is 5 or less, and particularly preferable is a laminated sheet in which layers A / layers B / layers A are sequentially laminated in three layers.
- the layer A containing a specific amount of polylactic acid and polybutylene succinate resin is included in at least one outermost layer, the impact on the inside of the sheet when impact is applied from the layer A side As a result, it has the effect of reducing propagation and improving the impact resistance of the entire laminated sheet. Therefore, it is important that the layer A is disposed on at least one outermost layer of the laminated sheet. Further, when the laminated sheet of the present invention is processed, a usage method in which an impact is applied from the layer A side. It is preferable to process with.
- the layer A is arranged on the outermost layer on both sides of the laminated sheet, there is no restriction on how to place the sheet when processing the laminated sheet of the present invention, so the laminated sheet of the present invention has both outermost layers. It is preferable that both form the layer A.
- a sheet having impact resistance equivalent to that of the laminated sheet of the present invention can be obtained by forming a single layer sheet containing polylactic acid and a polybutylene succinate resin.
- the laminated sheet of the present invention having impact resistance equivalent to impact resistance can increase the content of polylactic acid in the entire sheet as compared with a single layer sheet. Therefore, the laminated sheet of the present invention has excellent characteristics in terms of plantiness compared to a single-layer sheet having equivalent impact resistance. Therefore, it is important that the sheet of the present invention has a laminated structure.
- the above-mentioned plantiness represents the content ratio of polylactic acid in the entire sheet.
- Layer A of the laminated sheet of the present invention contains polylactic acid and a polybutylene succinate resin, and polylactic acid is 60% by mass or more and 97.5% by mass or less in 100% by mass of all components of layer A.
- the mass proportion of polylactic acid in 100% by mass of all components of layer A is referred to as Pa. Therefore, layer A of the laminated sheet of the present invention contains polylactic acid and a polybutylene succinate resin. It is important that Pa is 60 mass% or more and 97.5 mass% or less). If the polylactic acid is less than 60% by mass in 100% by mass of all the components of the layer A, the plant degree is lowered, and the advantage of using polylactic acid is diminished.
- the impact resistance of a lamination sheet may fall.
- the content of polylactic acid is preferably 80% by mass or more and 97.5% by mass or less in 100% by mass of all the components of the layer A, from the viewpoint of further imparting transparency while maintaining high impact resistance and plantiness. More preferably, it is 90% by mass or more and 95% by mass or less in 100% by mass of all the components of the layer A.
- the layer A of the laminated sheet of the present invention contains a polybutylene succinate resin as described above. Since the polybutylene succinate resin has relatively good compatibility with polylactic acid, it has an advantage that the transparency of polylactic acid is not greatly impaired. When layer A does not contain a polybutylene succinate resin, it is difficult to improve impact resistance while maintaining the transparency of polylactic acid and to maintain the biodegradability of the laminated sheet.
- the content of the polybutylene succinate resin is preferably 2.5% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less, with respect to 100% by mass of all the components of the layer A.
- the layer A of the laminated sheet of the present invention can contain additives such as an antioxidant described later and other components such as particles.
- the content of these other components is preferably 0.1% by mass or more and 30% by mass or less with respect to 100% by mass of all the components of the layer A.
- the laminated sheet of the present invention has the layer A in at least one outermost layer, so that the impact propagation to the inside of the sheet is reduced when an impact is applied from the layer A side. It has the effect of improving impact properties.
- the ratio Xa of the thickness of the layer A is 10 to 40% with respect to 100% of the entire laminated sheet thickness.
- Xa is larger than 40%, the plantiness of the entire sheet may be lowered, and transparency may be lowered. Further, when bending is performed, whitening occurs in the bent portion. End up.
- the thickness ratio Xa of the layer A is smaller than 10%, when an impact is applied from the layer A side when the laminated sheet of the present invention is processed, the propagation of the impact into the sheet is reduced. A sufficient effect cannot be obtained, and the effect of improving the impact resistance of the laminated sheet as a whole cannot be obtained. Further preferred Xa is 20 to 30%.
- the laminated sheet of the present invention reduces the impact propagation to the inside of the sheet when impact is applied from the layer A side by controlling Xa to 10 to 40%, resulting in improved impact resistance of the entire laminated sheet There is an effect to make.
- the layer B of the laminated sheet of the present invention contains polylactic acid and a polybutylene succinate-based resin, and polylactic acid is 90% by mass or more and 100% by mass in 100% by mass of all the components of the layer B.
- Pb the mass proportion of polylactic acid in 100% by mass of all components of layer B
- layer B of the laminated sheet of the present invention is composed of polylactic acid and polybutylene succinate
- Pb is 90 mass% or more and less than 100 mass%. If the polylactic acid is less than 90% by mass in 100% by mass of all the components of the layer B, the degree of planting is lowered and the advantage of using polylactic acid is diminished.
- the polylactic acid is preferably 95% by mass or more and less than 100% by mass in 100% by mass of all the components of the layer B, and more preferably. Is an aspect in which polylactic acid is 98% by mass or more and 99% by mass or less with respect to 100% by mass of all the components of layer B.
- layer B does not contain a polybutylene succinate resin
- the layer B of the laminated sheet of the present invention can contain additives such as an antioxidant described later and other components such as particles.
- the content of these other components is preferably 0.1% by mass or more and less than 10% by mass in 100% by mass of all the components of the layer B.
- the laminated sheet of the present invention has the effect of reducing the impact propagation to the inside of the sheet when an impact is applied from the layer A side by having the layer A in at least one outermost layer.
- the layer B can relieve the impact propagated from the outermost layer A to the inside of the sheet, and as a result, it has the effect of improving the impact resistance of the entire laminated sheet.
- the degree of plane orientation ⁇ P of the laminated sheet of the present invention is 0 or more and 0.002 or less.
- an oriented sheet that is, a laminated sheet having a plane orientation degree ⁇ P exceeding 0.002 as a molded product, especially when forming into a three-dimensional shape by a forming method such as vacuum forming or vacuum / pressure forming, There is a problem that the conditions are limited and the processing condition width becomes narrow.
- the plane orientation degree ⁇ P is more preferably 0.0005 or more and 0.001 or less.
- the method for setting the plane orientation degree ⁇ P of the laminated sheet to 0 or more and 0.002 or less is not particularly limited, and examples include a method of extruding from a T die and then cooling and solidifying with a casting roll at 30 to 40 ° C. it can.
- cold stretching such as biaxial stretching (stretching at a temperature below the melting point)
- the degree of plane orientation ⁇ P may be greater than 0.002.
- the polylactic acid used in the present invention is mainly composed of L-lactic acid and / or D-lactic acid, and the components derived from lactic acid are 70 mol% or more and 100 mol in 100 mol% of all monomer components constituting polylactic acid. % Or less, and homopolylactic acid consisting essentially of L-lactic acid and / or D-lactic acid is preferably used.
- the polylactic acid used in the present invention preferably has crystallinity.
- Polylactic acid has crystallinity when the polylactic acid is sufficiently crystallized under heating and then subjected to differential scanning calorimetry (DSC) measurement in an appropriate temperature range. Says that heat of fusion is observed.
- DSC differential scanning calorimetry
- 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 higher 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.
- homopolylactic acid having an optical purity of 88% has a melting point of about 145 ° C.
- homopolylactic acid having an optical purity of 75% has a melting point of about 120 ° C.
- homopolylactic acid with an optical purity lower than 70% does not show a clear melting point and is amorphous.
- the polylactic acid used in the present invention can 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 laminated sheet.
- the proportion of amorphous homopolylactic acid may be determined within a range that does not impair the effects of the present invention.
- at least one of the polylactic acids used includes polylactic acid having an optical purity of 95% or more.
- the mass average molecular weight of the polylactic acid used in the present invention is usually at least 50,000 or more, preferably 80,000 to 400,000, more preferably 100,000 to 300,000.
- the mass mean molecular weight of polylactic acid as used in the field of this invention means the molecular weight which measured by the gel solvent permeation chromatography (GPC) with the chloroform solvent, and was calculated by the polymethylmethacrylate (PMMA) conversion method.
- the mechanical properties of the laminated sheet of the present invention containing the polylactic acid can be improved, and the processed product comprising the laminated sheet of the present invention is further improved.
- the mechanical properties can also be improved.
- the polylactic acid 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-tetrabutylphosphonium sul
- copolymerization components it is preferable to select the component which has biodegradability among the above-mentioned copolymerization components according to a use.
- These copolymer components are preferably contained in an amount of 0 mol% to 30 mol% in 100 mol% of all monomer components constituting polylactic acid.
- the polybutylene succinate resin used in the laminated sheet of the present invention is polybutylene succinate or polybutylene succinate adipate having a large impact resistance improving effect and good compatibility with polylactic acid.
- the mass average molecular weight of the polybutylene succinate resin used in the present invention is preferably 100,000 to 300,000.
- the mass average molecular weight of the polybutylene succinate resin referred to in the present invention refers to a molecular weight measured by gel permeation chromatography (GPC) in a chloroform solvent and calculated by a polystyrene (PS) conversion method.
- polybutylene succinate resins examples include GsPla FZ91PD (trade name, product number; Mitsubishi Chemical) and Bionore # 3003 (trade name, product number; Showa Polymer).
- polybutylene succinate is 1-4 butanediol. And succinic acid.
- an antioxidant In the laminated sheet of the present invention, an antioxidant, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, an antistatic agent, and the like within a range not impairing the effects of the present invention.
- Various additives such as oxidizers, ion exchangers, crystal nucleating agents, color pigments, or lubricants may contain inorganic fine particles, organic particles, and organic lubricants as necessary, in order to effectively express the functions. Is preferably added to layer A. And these preferable content is 0.1 to 30 mass% in 100 mass% of all the components of the layer A.
- 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, quinocridone, thio Organic pigments such as indigo can be used.
- 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 Fine particles comprising various phosphates such as calcium phosphate and magnesium phosphate, various oxides such as aluminum oxide, titanium oxide and zirconium oxide, various salts such as lithium fluoride and the like can be used.
- 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.
- 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.
- Pb is preferably larger than Pa. That is, it is preferable that the mass ratio of the polylactic acid in the layer B in 100% by mass of all the components in the layer B is larger than the mass ratio of the polylactic acid in the layer A in 100% by mass of all the components in the layer A.
- the polybutylene succinate resin as the whole laminated sheet Therefore, there is a problem that the plant degree of the entire laminated sheet is lowered as compared with the sheet in the case where Pb is larger than Pa. Therefore, it is preferable that Pb is larger than Pa in the laminated sheet of the present invention.
- the two-dimensional centerline average roughness Ra on the surface of the layer A is preferably 0.1 ⁇ m or more and 0.6 ⁇ m or less.
- Ra is less than 0.1 ⁇ m, sheets laminated at the time of molding process may be blocked to cause feeding failure, which may reduce the processing efficiency.
- the visibility of the contents may be lowered or a fine printing process cannot be performed when a molded product is formed using a laminated sheet.
- the more preferable two-dimensional centerline average roughness Ra of the layer A is 0.1 ⁇ m or more and 0.4 ⁇ m or less.
- the Ra on the surface of the layer A can be controlled to 0.1 to 0.6 ⁇ m by adjusting the content of inorganic particles and organic particles.
- a method in which particles having an average particle diameter of 0.1 to 10 ⁇ m are contained on the surface of the layer A by about 0.5 to 1% by mass is preferable.
- the laminated sheet of the present invention preferably has a haze Ha of 1% to 15%.
- a molded product using such a laminated sheet is preferably used as a packaging container or a packaging sheet having high design properties such as excellent visibility of contents and good appearance as a product. be able to.
- Ha is less than 1%, the sheet is easily damaged, and the appearance may deteriorate when such a laminated sheet is used as a packaging container or packaging sheet. Is insufficient, and may not be preferable for practical use.
- the more preferable Ha of the laminated sheet of the present invention is 2% or more and 10% or less.
- the lower limit of the haze is 1% as described above, but if the lower limit of the haze is about 4%, it is a sufficient value for use in applications requiring transparency such as packaging containers and packaging sheets.
- the content of the polybutylene succinate resin is changed, the stacking ratio of the layer A and the layer B is changed, and Xa is controlled. It is possible to control by adding organic particles as required. More specifically, by setting Pa to 80% by mass or more and 97.5% by mass or less and Pb to 95% by mass or more and less than 100% by mass, Ha can be reduced to 15% or less. In order to bring Ha close to 1%, control can be performed by reducing Xa within a range of 10 to 40%.
- the whiteness of the laminated sheet is preferably 80% or more.
- a laminated sheet having a whiteness of less than 80% may not be able to impart whiteness, concealment, and design required for a magnetic stripe card, IC card, or the like.
- the upper limit of the whiteness is not particularly limited and is preferably as large as possible. However, an upper limit of about 100% is a realistic value that can be achieved, but if it is about 98%, it is sufficient as a characteristic when considering use as a magnetic stripe card, IC card, or the like.
- Pa is 60% by mass or more and less than 80% by mass
- Pb is 90% by mass or more and less than 95% by mass
- layer A and / or layer B It is preferable to contain inorganic particles. Suitable inorganic particles include magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zinc oxide, calcium carbonate, barium sulfate, magnesium carbonate, calcium silicate, talc, clay and the like. When such inorganic particles are contained, titanium oxide is preferable because of excellent concealability.
- the average particle diameter of the inorganic particles used for setting the whiteness to 80% or more is preferably 10 ⁇ m or less, more preferably 0.01 to 7 ⁇ m.
- the content of the inorganic particles in the layer A is preferably 2% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 20% by mass or less, based on 100% by mass of all the components of the layer A. is there. If the content is less than 2% by mass, the contribution to the whiteness and concealment of the laminated sheet may be small, while if it exceeds 35% by mass, the physical properties of the laminated sheet may be impaired.
- the content of the inorganic particles in the layer B is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass with respect to 100% by mass of all the components of the layer B. It is as follows. If the content is less than 0.5% by mass, the contribution to the whiteness and concealment of the laminated sheet may be small. May fade.
- the melt-kneading method is not particularly limited, and a commonly used 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 mixing order is not particularly limited, for example, a method in which polylactic acid and polybutylene succinate resin are dry blended and then supplied to a melt kneader, or a master batch in which polylactic acid and polybutylene succinate resin are melt kneaded in advance. And a method of melt-kneading the master batch and polylactic acid. In addition, if necessary, a method of melt-kneading other components at the same time, or a method of preparing a master batch in which polylactic acid and other additives are melt-kneaded in advance, and then melt-kneading the master batch and polylactic acid are used. Also good.
- the polylactic acid 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 such as lactide or glycolide, can also be used as a raw material.
- dicarboxylic acids and glycols can also be used.
- Polylactic acid 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.
- the laminated sheet of the present invention can be obtained by existing film production methods such as T-die casting method, inflation method, calendering method, etc.
- T-die casting that melt-kneads polylactic acid and extrudes using T-die The method is preferred.
- polylactic acid having a moisture content of 400 ppm or less is obtained by drying the chip at 60 to 110 ° C. for 3 hours or more, and the cylinder temperature at the time of melt kneading is 150 ° C.
- the range of ⁇ 240 ° C. is preferable, and the range of 200 ° C. to 220 ° C. is more preferable from the viewpoint of preventing deterioration of polylactic acid.
- the T die temperature is also preferably in the range of 200 ° C. to 220 ° C.
- a sheet having a thickness of about 0.1 mm to 1.0 mm is obtained by extruding from the T die and cooling with a cooling roll of 30 to 40 ° C. Get.
- 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 thickness of the laminated sheet of the present invention is not particularly limited, but is usually about 0.1 mm to 1.0 mm when considering use as a molded product.
- the thickness of the laminated sheet is usually about 0.15 mm to 0.7 mm, and the laminated sheet of the present invention is suitable for printed products.
- the laminated sheet is preferably about 0.1 mm to 0.4 mm in thickness.
- the laminated sheet of the present invention is excellent in moldability, it can be used as a molded product by processing.
- Examples of the molded article made of the laminated sheet of the present invention include containers, blister packs, printed products, cards, clear files and the like.
- a clear case, a desktop calendar case, and a clear file are suitable because an existing printing machine can be used and ruled lines can be processed while being transparent.
- a white use a card is suitable.
- a film sample was prepared in a size of 100 mm ⁇ 100 mm, and the measurement was performed 5 times per level. Furthermore, the impact value for each time was divided by the thickness of the measurement sample, and the impact value per unit thickness was obtained from the average value of five measurements. The sample thickness was measured with a digital micrometer. In addition, in the case of the sheet
- the impact value is 2.3 kN ⁇ m / mm or more, it is practical as a sheet for forming processing without cracking or burring in the processed part during punching.
- Haze Ha value (%) According to JIS-K-7105 (1981), the haze value was measured using a haze meter HGM-2DP type (manufactured by Suga Test Instruments Co., Ltd.). The measurement was performed three times per level, and was determined from the average value of the three measurements. In the case of the sheet having the layer A only on one of the outermost layers, the sample was set so that light was incident on the sheet from the surface on the layer A side.
- Transparency About the value measured by haze Ha value, it evaluated on the following references
- An ultra-thin section is prepared using a microtome so that the cross-section of the laminated sheet becomes the sample surface, and the sample is prepared by ion-sputtering Pt-Pd on the sample surface. Scanning by Hitachi, Ltd. Using an electron microscope S-800, a specific layer on the sample surface was observed and photographed at a magnification of 5000 times. An arbitrarily selected 50 mm ⁇ 50 mm image in the photograph was analyzed to determine the maximum diameter of each of the 10 particles, and the average diameter was measured to determine the average particle size of the particles in each layer.
- PB-1 Polybutylene succinate resin (Mitsubishi Chemical Corporation, trade name “GsPla” FZ91PD)
- PB-2 Polybutylene succinate resin (Mitsubishi Chemical Corporation, trade name “GsPla” FZ71PD)
- PB-3 Polybutylene succinate / adipate resin (made by Showa Polymer Co., Ltd., trade name “Bionore” # 3003)
- D-1 Master batch (silica average particle size: 3.2 ⁇ m) based on silica (10% by mass in 100% by mass of master batch) / PLA-1 (90% by mass in 100% by mass of master batch)
- D-2) Titanium oxide (25% by mass in 100% by mass of masterbatch), ethylenebisstearyl acid (2% by mass in 100% by mass of masterbatch), PLA-1 (73% by mass in 100% by mass of master chip) based masterbatch
- D-1 Master batch (silica average particle size: 3.2 ⁇ m) based on silica (10% by mass in 100% by mass
- Table 1 shows the evaluation results of the obtained sheet.
- Examples 2-5, 11-16, Comparative Examples 1-4, 8-9) Implemented in the same manner as in Example 1 except that the polylactic acid, polybutylene succinate-based resin constituting each layer, the types and blending ratios of the inorganic particle master batches, and the lamination configuration and thickness ratio of each layer were changed as shown in the table. did.
- Example 6 to 10 Change the polylactic acid, polybutylene succinate resin, inorganic particle masterbatch type and mixing ratio of each layer, and the layered structure and thickness ratio of each layer as shown in the table, and separate independent vent type biaxial Supplying to the extruder, melt-kneading while degassing the vacuum vent part, co-extrusion from the T-die die with the die temperature set at 220 ° C, with a rubber casting drum and a metal cooling casting drum cooled to 40 ° C
- the non-oriented sheet having a thickness of 0.35 mm was produced by sandwiching and cooling and solidifying.
- the evaluation results of the obtained sheet are shown in the table.
- (Comparative Example 5) Change the polylactic acid, polybutylene succinate resin, inorganic particle masterbatch type and mixing ratio of each layer, and the layered structure and thickness ratio of each layer as shown in the table, and separate independent vent type biaxial Supply to the extruder, melt knead while degassing the vacuum vent part, co-extrusion from the T die die set to a base temperature of 220 ° C, with a metal casting drum and a metal cooling casting drum cooled to 40 ° C
- the biaxial stretching method is 3.0 times in the longitudinal direction at 80 ° C and 3.4 times in the transverse direction, heat treated at 140 ° C, and biaxial with a thickness of 0.30 mm.
- a stretched sheet was prepared.
- the evaluation results of the obtained sheet are shown in the table.
- (Comparative Example 7) Change the types and blending ratios of polylactic acid and polybutylene succinate resin constituting each layer and the thickness ratio of each layer as shown in the table, and supply them to separate independent vent type twin screw extruders, and vacuum vent Melted and kneaded while degassing the part, co-extruded from a T die die set at a die temperature of 220 ° C., sandwiched between metal cooling casting drums cooled to 40 ° C., cooled and solidified, and a sheet having a thickness of 0.35 mm After making, it was embossed.
- the evaluation results of the obtained sheet are shown in the table.
- the laminated sheets of Examples 1 to 10 are excellent in any of the characteristics of any one of impact resistance, transparency, blocking resistance, ruled line processability, and plantiness in any sheet. Examples 3, 5, 7, and 8 were excellent.
- the laminated sheets of Examples 11 to 16 are excellent in any one of the characteristics of impact resistance, whiteness, blocking resistance, ruled line processability, and plantiness in any of the sheets, In particular, Examples 12 and 14 were excellent.
- each sheet was inferior in one or more of the characteristics of impact resistance, blocking resistance, ruled line workability, and plantiness, and there was a clear difference from the examples. .
- [Molded product creation] The laminated sheets obtained in Examples 5, 7, and 8 and Comparative Examples 1, 4, 5, and 6 were punched and bent. The processing evaluation results are summarized in a table.
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Abstract
Description
(1)層Aを少なくとも一方の最外層に有し、層Bを内層に有する、少なくとも3層からなる積層シートであり、
層Aは、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Aの全成分100質量%においてポリ乳酸が60質量%以上97.5質量%以下であり(以下、層Aの全成分100質量%におけるポリ乳酸の質量割合をPaという)、かつ、層Aの厚みの割合Xaが、積層シートの全体厚さ100%に対して10~40%であり、
層Bは、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Bの全成分100質量%においてポリ乳酸が90質量%以上100質量%未満であり(以下、層Bの全成分100質量%におけるポリ乳酸の質量割合をPbという)、
面配向度ΔPが0以上0.002以下であることを特徴とする、積層シート。
(2)前記Pbが前記Paよりも大きいことを特徴とする、前記(1)に記載の積層シート。
(3)前記層A表面の2次元中心線平均粗さRaが、0.1μm以上0.6μm以下であることを特徴とする前記(1)又は(2)に記載の積層シート。
(4)ヘイズHa(%)が、1%以上15%以下であることを特徴とする前記(1)~(3)のいずれかに記載の積層シート。
(5)白色度が80%以上であることを特徴とする前記(1)~(3)のいずれかに記載の積層シート。
(6)前記(1)~(5)のいずれかに記載の積層シートからなる成形品。
[測定及び評価方法]
実施例中に示す測定や評価は次に示すような条件で行った。
(1)シート厚み
厚みをシート全幅に対して、マイクロゲージで10点測定し、10点の平均値t(mm)を求めて、シート厚みとした。
(2)耐衝撃性:インパクト値(kN・m/mm)
フィルムインパクトテスター(東洋精機製作所製)により、直径1/2インチ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値の測定を行った。100mm×100mmにフィルムサンプルを作製し、測定は1水準につき5回行った。さらに、1回毎のインパクト値を測定サンプル厚みで割り返し、単位厚みあたりのインパクト値とし、5回の測定の平均値から求めた。サンプル厚みは、デジタル式マイクロメーターで測定した。なお、最外層の一方にのみ層Aを有するシートの場合は、層Aの側の面から衝撃がシートに加わるように、サンプルをセットした。
(3)ヘイズHa値(%)
JIS-K-7105(1981年)に準じて、ヘイズメーターHGM-2DP型(スガ試験機社製)を用いてヘイズ値を測定した。測定は1水準につき3回行い、3回の測定の平均値から求めた。なお、最外層の一方にのみ層Aを有するシートの場合は、層Aの側の面から光がシートに入射するように、サンプルをセットした。
(4)透明性
(3)ヘイズHa値で測定した値について、以下の基準で評価した。
◎(優):Haが10%以下の積層シート
○(良):Haが10%を超え15%以下の積層シート
△(その他):Haが15%を超える積層シート
(5)白色度
測定面は層A側とし、分光式色差計SE-2000(日本電色工業(株)製)を用いてL,a,b値を求め、JIS-L-1015(1999年) C法に従い、下式を用いて白色度を求めた。
白色度(%)=100-[(100-L)2+a2+b2]1/2
測定は1水準につき3回行い、3回の測定の平均値から求めた。
(6)中心線平均粗さ:Ra
JIS-B-0601(2001年)に準じて、万能表面形状測定器SE-3FA((株)小坂研究所製)により2次元中心線平均粗さ(Ra)を測定した。なお、測定条件は、触針先端半径:2μm、測定力:0.7mN、測定長25mm、カットオフ:0.08mmである。なお、最外層が共に層Aを有するシートの場合には、両面の中心線平均粗さを測定し、その値が大きい方を表に記した。
(7)耐ブロッキング性
シートを10枚積層し、上から4kgの荷重をかけ40℃×24hrにて処理後のシートの剥離性を観察した。なお、最外層の一方にのみ層Aを有するシートの場合は、シートの向きを統一して重ねた(つまり、シートの異なる面同士が接するように重ねた。)。
○(良):全てのシートを容易に剥離可能であり、実用上問題なし。
△(可):剥離可能であり、実用上問題なし。
×(不可):剥離時にブロッキングしていたり、剥離しにくい箇所があった。実用不可。
(8)罫線加工性
シートに罫線刃を入れ、折り曲げ罫線加工を施し、罫線を軸にして折り曲げを5往復したときの折り曲げ部を観察した。なお、最外層の一方にのみ層Aを有するシートの場合は、層Aの側から罫線刃を入れた。
○(良):折り曲げ部で破断・亀裂・白化が発生せず、問題なし。
×(不可):折り曲げ部で破断・亀裂・白化が発生した。
(9)面配向度ΔP
王子計測機器(株)社製自動複屈折計KOBRA-21ADHを用いて、シート状サンプルの3主軸方向に関する複屈折Δx、Δy、Δzを求め、Δx=γ-β、Δy=γ-α、Δz=α-β(γ≧β、αはシートの厚さ方向の屈折率)の関係より面配向度ΔPを下記の式から求めた。なお、最外層の一方にのみ層Aを有するシートの場合は、層Aの側の面から光がシートに入射するように、サンプルをセットした。
ΔP={(γ+β)/2}-α=(Δy-Δz)/2
(10)平均粒径
積層シートの断面がサンプル面となるようミクロトームを使用して超薄切片を作成し、サンプル表面にPt-Pdをイオンスパッタしてサンプルを調整し、日立製作所社製の走査電子顕微鏡S-800を用い、5000倍でサンプル表面の特定の層の観察、写真撮影を行った。その写真中の任意に選択した50mm×50mmの画像を分析して10個の粒子について各々の最大直径を求め、これを平均することにより、測定した各層中の粒子の平均粒径を測定した。
(11)積層比
積層シートの断面がサンプル面となるようミクロトームを使用して超薄切片を作成し、サンプル表面にPt-Pdをイオンスパッタしてサンプルを調整し、日立製作所社製の走査電子顕微鏡S-800を用い、250倍でサンプル表面の観察、写真撮影を行った。その写真にて各層の厚み比を測定した。
(12)積層シートの植物度
積層シートの、各層のポリ乳酸の含有割合(重量%)、層構成、ならびに厚み比から、積層シート全体100質量%に対するポリ乳酸の含有割合(植物度)を求め、以下の基準にて判断した。
◎(優):植物度が90質量%以上
○(良):植物度が80質量%以上90質量%未満
×(不可):植物度が80質量%未満
(13)成形品加工評価
得られたシートに打抜きおよび曲げ加工を施し、実用性能を以下の基準にて判断した。
○(良):実用上問題なく使用できる。
×(不可):割れやバリが発生し、実用上問題あり、使用不可。
○(良):実用上問題なく使用できる。
×(不可):曲げ部での白化発生や、90°の角度に折り曲げできず、実用上問題あり、使用不可。
[使用したポリ乳酸]
(PLA-1):
ポリD-乳酸含有割合5.0mol%、融点150℃、PMMA換算の質量平均分子量22万のポリL-乳酸樹脂。(Nature Works社製)
[使用したポリブチレンサクシネート系樹脂]
(PB―1):
ポリブチレンサクシネート樹脂(三菱化学社製、商品名“GsPla”FZ91PD)
(PB―2):
ポリブチレンサクシネート樹脂(三菱化学社製、商品名“GsPla”FZ71PD)
(PB―3):
ポリブチレンサクシネート・アジペート系樹脂(昭和高分子社製、商品名“ビオノーレ”#3003)
[使用した無機粒子マスターバッチ]
(D―1):
シリカ(マスターバッチ100質量%において10質量%)・PLA-1(マスターバッチ100質量%において90質量%)ベースのマスターバッチ(シリカ平均粒径:3.2μm)
(D―2):
酸化チタン(マスターバッチ100質量%において25質量%)・エチレンビスステアリル酸(マスターバッチ100質量%において2質量%)・PLA―1(マスターチップ100質量%において73質量%)ベースのマスターバッチ(酸化チタン平均粒径:0.2μm)
[ポリ乳酸系樹脂フィルムの作成]
(実施例1)
層A用として、ポリ乳酸(PLA-1)、ポリブチレンサクシネート系樹脂(PB-1)を90:10の比率で、また層B用として、ポリ乳酸(PLA-1)、ポリブチレンサクシネート系樹脂(PB-1)を98:2の比率で、それぞれ独立した別々のベント式二軸押出機に供給し、真空ベント部を脱気しながら溶融混練し、口金温度を220℃に設定したTダイ口金より共押出し、表面温度が40℃に温度調節された金属製キャスティングドラム同士で挟み冷却固化し、層A/層B/層Aが10:80:10、厚み0.35mmの無配向シートを作製した。
各層を構成するポリ乳酸、ポリブチレンサクシネート系樹脂、無機粒子マスターバッチの種類と配合比率、及び、各層の積層構成や厚み比率を、表のように変えた以外は実施例1と同様に実施した。
(実施例6~10、比較例6)
各層を構成するポリ乳酸、ポリブチレンサクシネート系樹脂、無機粒子マスターバッチの種類と配合比率、及び、各層の積層構成や厚み比率を、表のように変え、それぞれ独立した別々のベント式二軸押出機に供給し、真空ベント部を脱気しながら溶融混練し、口金温度を220℃に設定したTダイ口金より共押出し、ゴム製キャスティングドラムと、40℃に冷却した金属製冷却キャスティングドラムで挟み、冷却固化し、厚み0.35mmの無配向シートを作製した。
(比較例5)
各層を構成するポリ乳酸、ポリブチレンサクシネート系樹脂、無機粒子マスターバッチの種類と配合比率、及び、各層の積層構成や厚み比率を、表のように変え、それぞれ独立した別々のベント式二軸押出機に供給し、真空ベント部を脱気しながら溶融混練し、口金温度を220℃に設定したTダイ口金より共押出し、金属製キャスティングドラムと、40℃に冷却した金属製冷却キャスティングドラムで挟み、冷却固化し、た後、逐次二軸延伸方で縦方向に80℃で3.0倍、横方向に3.4倍延伸し、140℃で熱処理を行い、厚み0.30mmの二軸延伸シートを作製した。
(比較例7)
各層を構成するポリ乳酸、ポリブチレンサクシネート系樹脂の種類と配合比率、及び、各層の厚み比率、を表のように変え、それぞれ独立した別々のベント式二軸押出機に供給し、真空ベント部を脱気しながら溶融混練し、口金温度を220℃に設定したTダイ口金より共押出し、40℃に冷却した金属製冷却キャスティングドラム同士で挟み、冷却固化し、厚み0.35mmのシートを作製した後、エンボス加工を施した。
得られたシートの評価結果を表に示した。
[成形品作成]
実施例5、7、8および比較例1、4、5、6で得られた積層シートに打ち抜きと曲げ加工を施した。加工評価結果を表にまとめた。
Claims (6)
- 層Aを少なくとも一方の最外層に有し、層Bを内層に有する、少なくとも3層からなる積層シートであり、
層Aは、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Aの全成分100質量%においてポリ乳酸が60質量%以上97.5質量%以下であり(以下、層Aの全成分100質量%におけるポリ乳酸の質量割合をPaという)、かつ、層Aの厚みの割合Xaが、積層シートの全体厚さ100%に対して10~40%であり、
層Bは、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Bの全成分100質量%においてポリ乳酸が90質量%以上100質量%未満であり(以下、層Bの全成分100質量%におけるポリ乳酸の質量割合をPbという)、
面配向度ΔPが0以上0.002以下であることを特徴とする積層シート。 - 前記Pbが前記Paよりも大きいことを特徴とする、請求項1に記載の積層シート。
- 前記層A表面の2次元中心線平均粗さRaが、0.1μm以上0.6μm以下であることを特徴とする請求項1又は2に記載の積層シート。
- ヘイズHa(%)が、1%以上15%以下であることを特徴とする請求項1~3のいずれかに記載の積層シート。
- 白色度が80%以上であることを特徴とする請求項1~3のいずれかに記載の積層シート。
- 請求項1~5のいずれかに記載の積層シートからなる成形品。
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CN201080011119.9A CN102348553B (zh) | 2009-03-12 | 2010-02-23 | 聚乳酸系叠层片 |
US13/203,016 US20110311770A1 (en) | 2009-03-12 | 2010-02-23 | Polylactic acid-based multilayer sheet |
JP2010508541A JP5594135B2 (ja) | 2009-03-12 | 2010-02-23 | ポリ乳酸系積層シート |
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KR200470687Y1 (ko) * | 2010-03-15 | 2014-01-07 | (주)엘지하우시스 | 바이오 폴리머 수지를 구비하는 바닥재 |
JP2015107602A (ja) * | 2013-12-05 | 2015-06-11 | 電気化学工業株式会社 | 積層シート及び成形容器 |
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DE102013017927A1 (de) * | 2013-10-28 | 2015-04-30 | Giesecke & Devrient Gmbh | Verfahren zur Herstellung einer Folie und eines tragbaren Datenträgers |
KR102509613B1 (ko) * | 2019-12-23 | 2023-03-14 | 주식회사 알앤에프케미칼 | 신장율이 우수한 생분해성 자기점착 보호필름 |
KR102509611B1 (ko) * | 2019-12-23 | 2023-03-14 | 주식회사 알앤에프케미칼 | 생분해성 자기점착 보호필름 |
KR102509608B1 (ko) * | 2019-12-23 | 2023-03-14 | 주식회사 알앤에프케미칼 | 생분해성 자기점착 보호필름 |
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KR20110127149A (ko) | 2011-11-24 |
TWI480161B (zh) | 2015-04-11 |
CN102348553B (zh) | 2015-12-09 |
CN105415825A (zh) | 2016-03-23 |
TW201038402A (en) | 2010-11-01 |
JPWO2010103915A1 (ja) | 2012-09-13 |
JP5594135B2 (ja) | 2014-09-24 |
CN102348553A (zh) | 2012-02-08 |
US20110311770A1 (en) | 2011-12-22 |
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EP2407305A4 (en) | 2014-01-08 |
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