Polyester film, and laminate, packaging, food and beverage packaging, cosmetic packaging, pharmaceutical / quasi-pharmaceutical packaging, and product
By using a polyester resin film with a specific composition, the problem of adsorption of organic compounds by sealing films has been solved, resulting in a polyester film with high sealing strength and low adsorption, suitable for food, beverage, cosmetic and pharmaceutical packaging, ensuring drug efficacy and food quality.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-19
- Publication Date
- 2026-06-26
Smart Images

Figure CN122295423A_ABST
Abstract
Description
[0001] Related applications
[0002] This application claims priority to Japanese Patent Application No. 2023-200241, filed on November 27, 2023, and incorporates all the contents described in that Japanese application. Technical Field
[0003] This invention relates to polyester films, and laminates, packaging bodies, food and beverage packaging bodies, cosmetic packaging bodies, pharmaceutical / quasi-pharmaceutical packaging bodies, and products comprising said polyester films. Background Technology
[0004] Sealing films have long been used in the packaging of food and beverage products, cosmetics, pharmaceuticals / quasi-pharmaceuticals, etc. As sealing films, polyolefin resins such as polyethylene or polypropylene are sometimes used, for example. Additionally, for example, packaging bags for patch storage with polyacrylonitrile as a heat-sealing layer have been proposed (see, for example, Patent Document 1).
[0005] Existing technical documents
[0006] Patent documents
[0007] Patent Document 1: Japanese Patent Application Publication No. 2005-328928 Summary of the Invention
[0008] The problem the invention aims to solve
[0009] Typically, sealing films are formed by heat-pressing the films together to create a package for packaging the contents. Therefore, it is required that one side of the sealing film (the heat-sealed surface) does not readily absorb organic compounds from the packaged contents.
[0010] Not easily adsorbed
[0011] The polyacrylonitrile resin described in the aforementioned patent document 1 is expensive and has the problem that even when used in a heat-sealing layer, it cannot achieve good sealing strength.
[0012] In addition, while polyolefin resins such as polyethylene and polypropylene have excellent sealing strength, they easily adsorb organic compounds, such as the active ingredients in pharmaceuticals like camphor and menthol, and flavoring ingredients in foods like limonene. If polyolefin resins are used in layers that come into direct contact with pharmaceuticals and food, there may be issues such as reduced efficacy of the pharmaceuticals or changes in the aroma and taste of the food.
[0013] Therefore, the current situation is that there is no polyester film that has low adsorption of organic compounds in the packaged goods and high sealing strength.
[0014] The purpose of this invention is to provide a polyester film with low adsorption of organic compounds in the packaged product and high sealing strength, as well as a laminate containing the above-mentioned polyester film, a package, a food and beverage package, a cosmetic package, a pharmaceutical / quasi-pharmaceutical package, and a product.
[0015] Solution for solving the problem
[0016] The means to solve the above problems are as follows.
[0017] The polyester film of the present invention comprises: a first polyester resin including a first acid unit and a first alcohol unit. The first acid unit comprises terephthalic acid units at a total amount of 90 mol% or more relative to the total amount of the first acid units. The first alcohol unit comprises ethylene glycol units at a total amount of 50 mol% or more relative to the total amount of the first alcohol units, 2,2-dimethyl-1,3-propanediol units at a total amount of 5 mol% to 40 mol% and diethylene glycol units at a total amount of 0.1 mol% to 5 mol%. The content of the first polyester resin is 80% by mass or more relative to the total amount of the polyester film. The thickness of the polyester film is 25 μm to 100 μm.
[0018] In one embodiment of the polyester film of the present invention, it is preferable that the enthalpy of fusion (ΔHm) calculated by integrating the endothermic peak at 220°C to 260°C when the temperature is increased from 25°C to 300°C at a heating rate of 10°C / min in the differential scanning calorimetry (DSC) measurement of the polyester film is 10 J / g or less.
[0019] In one embodiment of the polyester film of the present invention, it is preferable that the tear strength of the polyester film obtained by tensile testing at 23°C and 200 mm / min is 2 N / mm to 15 N / mm in both the length and width directions.
[0020] In one embodiment of the polyester film of the present invention, it is preferable that the elastic modulus obtained by tensile testing the polyester film at 23°C and 50 mm / min is 1.6 kN / mm in both the length and width directions. 2 ~2.2kN / mm 2 .
[0021] In one embodiment of the polyester film of the present invention, it is preferable that the heat shrinkage rate of the polyester film before and after heat treatment in hot air at 90°C for 3 minutes is less than 10% in both the length and width directions.
[0022] In one embodiment of the polyester film of the present invention, when two polyester films 1 and 2 are heat-pressed together at 130°C to 150°C, 0.2 MPa, and for 2 seconds, the sealing strength between polyester film 1 and polyester film 2 is 15 N / 15 mm to 50 N / 15 mm.
[0023] In one embodiment of the polyester film of the present invention, it is preferable to determine the initial mass of test pieces obtained by cutting the polyester film into 4cm × 4cm squares, add the test pieces to a beaker, add 5ml of limonene, cover the beaker and store it at 25°C for 7 days, and then determine the mass of the test pieces. The difference between the initial mass A and the mass B after 7 days (BA) is the adsorption capacity of limonene, which is 0.2mg / cm³. 2 the following.
[0024] In one embodiment of the polyester film of the present invention, the polyester film is preferably an unstretched material.
[0025] In one embodiment of the polyester film of the present invention, the first polyester resin preferably further comprises a crosslinking agent unit.
[0026] In one embodiment of the polyester film of the present invention, the first acid unit preferably further comprises trimellitic acid units in an amount of 0.05 mol% to 5 mol% relative to the total amount of the first acid unit.
[0027] In one embodiment of the polyester film of the present invention, it is preferable to further contain 0.05% to 1% by mass of an anti-blocking agent.
[0028] In one embodiment of the polyester film of the present invention, it preferably has a first layer and a second layer, wherein the first layer contains a first polyester resin comprising 80% or more of a first polyester resin relative to the first layer and a second polyester resin comprising less than 20% of a second polyester resin relative to the first layer, and the second layer contains 90% or more of a first polyester resin relative to the second layer.
[0029] In one embodiment of the polyester film of the present invention, the first layer preferably further contains an anti-blocking agent in an amount of 0.05% to 1% by mass relative to the first layer.
[0030] In one embodiment of the polyester film of the present invention, a third layer is preferably provided between the first layer and the second layer, the third layer comprising: a first polyester resin comprising 80% or more of the mass of the third layer, and a second polyester resin comprising less than 20% of the mass of the third layer.
[0031] In one embodiment of the polyester film of the present invention, the third layer preferably further contains an anti-blocking agent in an amount of 0.05% to 1% by mass relative to the third layer.
[0032] The laminate of the present invention has a substrate film and a sealing layer. The sealing layer comprises the polyester film of the present invention.
[0033] The packaging body of the present invention has the polyester film of the present invention, at least a portion of which is fused together.
[0034] The food and beverage packaging of the present invention comprises the polyester film of the present invention and the food and beverage covered by the polyester film.
[0035] The cosmetic packaging of the present invention comprises the polyester film of the present invention and the cosmetic product covered by the polyester film.
[0036] The pharmaceutical / quasi-pharmaceutical packaging of the present invention comprises the polyester film of the present invention and the pharmaceutical / quasi-pharmaceutical covered by the polyester film.
[0037] The product of the present invention comprises: a package containing an organic compound, and a polyester film of the present invention for packaging the package, at least a portion of the polyester film being fused together.
[0038] In one embodiment of the product of the present invention, the preferred organic compound is selected from limonene, camphor, menthol, methyl salicylate, tocopheryl acetate, isopropyl methylphenol, ketoprofen, ketoprofen sodium, diclofenac sodium, felbinac, loxoprofen sodium, tulobuterol, rivastigmine, chlorpromazine hydrochloride, haloperidol, risperidone, paliperidone, blananserin, perospirone hydrochloride hydrate, lurasidone hydrochloride, olanzapine, and quetiapine fumarate. At least one of the following: Fumarate, Asenapine Maleate, Clozapine, Aripiprazole, and Brexpiprazole.
[0039] The effects of the invention
[0040] According to the present invention, a polyester film with low adsorption to organic compounds in the packaged item and high sealing strength can be provided, as well as a laminate containing the above-mentioned polyester film, a package, a food and beverage package, a cosmetic package, a pharmaceutical / quasi-pharmaceutical package, and a product. Attached Figure Description
[0041] Figure 1 This is a schematic diagram illustrating an example of the polyester film of the present invention.
[0042] Figure 2 This is a schematic diagram illustrating another example of the polyester film of the present invention.
[0043] Figure 3 This is a schematic diagram illustrating another example of the polyester film of the present invention. Detailed Implementation
[0044] (Polyester film)
[0045] The polyester film of the present invention contains a first polyester resin comprising a first acid unit and a first alcohol unit, preferably a second polyester resin and an anti-blocking agent, and further contains other components as needed.
[0046] The polyester film of the present invention comprises: a first polyester resin comprising a first acid unit and a first alcohol unit, wherein the first acid unit comprises terephthalic acid units comprising 90 mol% or more of the total amount of the first acid unit. The first alcohol unit comprises ethylene glycol units comprising 50 mol% or more of the total amount of the first alcohol unit, 2,2-dimethyl-1,3-propanediol units comprising 5 mol% to 40 mol% of the total amount of the first alcohol unit, and diethylene glycol units comprising 0.1 mol% to 5 mol% of the total amount of the first alcohol unit. By satisfying the conditions (1) and (2) below, it is possible to have low adsorption capacity for organic compounds in the packaged product and to have high sealing strength.
[0047] (1) The content of the first polyester resin is more than 80% by mass relative to the total amount of polyester film.
[0048] (2) The thickness of the polyester film is 25μm~100μm.
[0049] Furthermore, the polyester film of the present invention contains: a first polyester resin comprising a first acid unit and a first alcohol unit, wherein the first acid unit comprises terephthalic acid units comprising 90 mol% or more of the total amount of the first acid unit. The first alcohol unit comprises ethylene glycol units comprising 50 mol% or more of the total amount of the first alcohol unit, 2,2-dimethyl-1,3-propanediol units comprising 5 mol% to 40 mol% of the total amount of the first alcohol unit, and diethylene glycol units comprising 0.1 mol% to 5 mol% of the total amount of the first alcohol unit. In addition to satisfying the conditions of (1) and (2) above, it is preferable to satisfy at least one of the conditions of (3) to (9) below, and more preferably to satisfy all of (1) to (9). This enables the film to have low adsorption of organic compounds in the packaged item, high sealing strength, and excellent tearability and shapeability.
[0050] Here, tearability refers to the ease with which the packaging can be cut by hand when opened. Shapeability refers to the ease with which the film can be processed during lamination, bag making, deep drawing, and other processes.
[0051] In addition, polyolefin resin films have a low elastic modulus, resulting in poor tearability.
[0052] In addition, unstretched A-PET films using crystalline PET resin have excellent sealing strength and low adsorption of organic compounds, but they also have the problems of high melt entropy and poor tearability.
[0053] In addition, biaxially stretched polyethylene terephthalate films have excellent sealing strength, low adsorption to organic compounds, and hand-tearability, but they have the problem of poor excipientability.
[0054] The polyester film of the present invention can solve the problems of the above-mentioned existing resin films.
[0055] (3) In the differential scanning calorimetry (DSC) of the polyester film, the enthalpy of fusion (ΔHm) calculated by integrating the endothermic peak at 220°C to 260°C when the temperature is increased from 25°C to 300°C at a heating rate of 10°C / min is less than 10 J / g.
[0056] (4) The tear strength of the polyester film obtained by tensile testing at 23°C and 200 mm / min is 2 N / mm to 15 N / mm in both the length and width directions.
[0057] (5) The elastic modulus of the polyester film, determined by tensile testing at 23°C and 50 mm / min, is 1.6 kN / mm in both the length and width directions. 2 ~2.2kN / mm 2 .
[0058] (6) The heat shrinkage rate of the polyester film before and after the heat treatment is less than 10% in both the length and width directions when the film is heated in hot air at 90°C for 3 minutes.
[0059] (7) When two polyester films 1 and 2 are heat-pressed together at 130℃~150℃, 0.2MPa and 2 seconds, the sealing strength between the polyester film 1 and the polyester film 2 is 15N / 15mm~50N / 15mm.
[0060] (8) Determine the initial mass of test pieces obtained by cutting the polyester film into 4cm×4cm squares. Add the test pieces to a beaker, add 5ml of limonene, cover the beaker, and store at 25°C for 7 days. Then, determine the mass of the test pieces. The difference between the initial mass A and the mass B after 7 days (BA) is the adsorption capacity of limonene, which is 0.2mg / cm³. 2 the following.
[0061] (9) The polyester film is an unstretched material.
[0062] Here, the conditions (1) to (9) above will be explained in detail.
[0063] (1) The content of the first polyester resin relative to the total amount of polyester film is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 93% by mass or more, even more preferably 96% by mass or more, particularly preferably 98% by mass or more, and even more particularly preferably 100% by mass. If the content of the first polyester resin is less than 80% by mass, it may sometimes be deteriorated by the low adsorption of organic compounds in the packaging and / or the tearability of the polyester film.
[0064] (2) The thickness of the polyester film is 25μm to 100μm, preferably 25μm to 90μm, more preferably 25μm to 80μm, even more preferably 30μm to 80μm, even more preferably 30μm to 70μm, particularly preferably 30μm to 60μm, and even more particularly preferably 30μm to 50μm. If the thickness of the polyester film is less than 25μm, the sealing strength is reduced, and sometimes its function as a packaging material is reduced. If it exceeds 100μm, sometimes its adsorption capacity to organic compounds in the packaged goods becomes higher.
[0065] The thickness of the polyester film is the average value obtained by measuring the thickness of any 5 points of the polyester film with a micrometer.
[0066] (3) In the differential scanning calorimetry (DSC) measurement of the polyester film of the present invention, the enthalpy of melting (ΔHm) calculated by integrating the endothermic peak at 220°C to 260°C when the temperature is increased from 25°C to 300°C at a heating rate of 10°C / min is preferably 10 J / g or less, more preferably 5 J / g or less, even more preferably 2 J / g or less, and particularly preferably 0 J / g (no peak value). If the enthalpy of melting (ΔHm) exceeds 10 J / g, the tearability of the unstretched polyester film may sometimes be poor.
[0067] (4) In the polyester film of the present invention, the tear strength obtained by performing a tensile test on the polyester film at 23°C and 200 mm / min is preferably 2N / mm to 15N / mm in both the length and width directions, more preferably 5N / mm to 15N / mm, even more preferably 7N / mm to 15N / mm, and particularly preferably 10N / mm to 15N / mm.
[0068] The length direction is sometimes also referred to as the longitudinal direction (machine direction, MD direction).
[0069] The width direction is sometimes also referred to as the transverse direction (TD direction).
[0070] Tear strength can be determined, for example, according to JIS K7128-1 "Test method for tear strength of plastic films and sheets - Part 1: trouser tear method".
[0071] (5) In the polyester film of the present invention, the elastic modulus determined by tensile testing of the polyester film at 23°C and 50 mm / min is preferably 1.6 kN / mm in both the length and width directions. 2 ~2.2kN / mm 2 More preferably, it is 1.6 kN / mm 2 ~2.1kN / mm 2 The optimal value is 1.6 kN / mm. 2 ~2.0kN / mm 2 A further preferred value is 1.7 kN / mm. 2 ~2.0kN / mm 2 The preferred value is 1.8 kN / mm. 2 ~2.0kN / mm 2 If the elastic modulus is less than 1.6 kN / mm 2 Sometimes, the tearability is poor, especially if it exceeds 2.2 kN / mm. 2 If it is not in a certain condition, it requires a large force during deep drawing and other processing, and therefore sometimes has poor shapeability.
[0072] The length direction is sometimes also referred to as the longitudinal direction (machine direction, MD direction).
[0073] The width direction is sometimes also referred to as the transverse direction (TD direction).
[0074] The modulus of elasticity can be determined, for example, according to ISO 527-3:2012.
[0075] (6) In the polyester film of the present invention, the heat shrinkage rate before and after heat treatment when the polyester film is heated in hot air at 90°C for 3 minutes is preferably 10% or less in both the length and width directions, more preferably 5% or less, further preferably 3% or less, even more preferably 2% or less, particularly preferably 1% or less, and may also be 0% (no dimensional change). If the heat shrinkage rate exceeds 10%, wrinkles may sometimes occur during processing such as lamination, packaging, and deep drawing.
[0076] The heat shrinkage rate is determined by placing test pieces cut from polyester film to a specified size in a forced-air oven heated to 90°C and allowing them to stand for 3 minutes. The length (MD) and width (TD) directions (AM, AT) of the test pieces are measured before standing. After 3 minutes, the test pieces are removed from the forced-air oven, and the lengths in the MD and TD directions (BM, BT) are measured. Based on the measured lengths AM and BM in the MD direction, the heat shrinkage rate (%) in the MD direction can be calculated as [(AM-BM) / AM] × 100. Conversely, the heat shrinkage rate (%) in the TD direction can be calculated as [(AT-BT) / AT] × 100 based on the measured lengths AT and BT in the TD direction.
[0077] (7) In the polyester film of the present invention, when two polyester films 1 and 2 are heat-pressed together at 130°C to 150°C, 0.2 MPa, and for 2 seconds, the sealing strength of polyester film 1 and polyester film 2 is preferably 15N / 15mm to 50N / 15mm, more preferably 15N / 15mm to 45N / 15mm, even more preferably 15N / 15mm to 40N / 15mm, even more preferably 15N / 15mm to 35N / 15mm, particularly preferably 15N / 15mm to 30N / 15mm, even more particularly preferably 16N / 15mm to 30N / 15mm, and even more particularly preferably 17N / 15mm to 30N / 15mm. If the sealing strength is less than 15N / 15mm, the airtightness of the packaging may sometimes decrease. Higher sealing strength is preferred, but currently 50N / 15mm is the upper limit.
[0078] In existing technologies, sealing strength is typically measured at a sealing temperature of 160°C. However, in this invention, sealing strength is measured at a lower sealing temperature of 130°C to 150°C. Generally, sealing strength tends to increase with increasing sealing temperature. Furthermore, it offers the following advantages: at lower sealing temperatures, energy efficiency during sealing is good, and environmental impact and cost can be reduced.
[0079] (8) In the polyester film of the present invention, the initial mass of a test piece obtained by cutting the polyester film into 4cm×4cm squares is determined. The test piece is added to a beaker, 5ml of limonene is added, the beaker is covered, and it is stored at 25°C for 7 days. The mass of the test piece is then measured. The difference between the initial mass A and the mass B after 7 days (BA), i.e., the adsorption capacity of limonene, is preferably 0.2mg / cm³. 2 The following is more preferably 0.1 mg / cm³ 2 Hereinafter, 0.05 mg / cm³ is further preferred. 2 The following can also be 0 mg / cm³ 2 (No adsorption of limonene).
[0080] (9) In the polyester film of the present invention, the polyester film is preferably an unstretched material. An unstretched material refers to a polyester film that has not undergone stretching treatment during the manufacturing process. This can be confirmed by the fact that the tensile elongation at break obtained by performing a tensile test at 23°C and 10 mm / min is 200% or more in both the length and width directions.
[0081] Unstretched materials (unstretched films) can achieve high sealing strength even at sealing temperatures over a wide temperature range, such as 130°C to 150°C. Furthermore, by forming an unstretched film, thermal shrinkage in the stretching direction can be prevented. As a result, wrinkles are less likely to form when heat is applied to the unstretched film, improving its processability.
[0082] The composition of the first polyester resin and the second polyester resin in the polyester film of the present invention, the manufacturing method of the polyester resin, and other components will be described in detail below.
[0083] The composition of the first and second polyester resins may not always be the same as that of the raw material monomers. This is especially true when ethylene glycol is used as the alcohol component, as it may include diethylene glycol as a byproduct. Hereafter, unless explicitly stated otherwise, expressions indicating the molar percentage concentration of the composition refer not to the amount of raw material monomers fed, but to the molar percentage concentration of the components present in the produced polyester resin.
[0084] In this invention, unless otherwise specified, the first and second polyester resins may also comprise molded articles. The polyester resin is a copolymer of acid units (polycarboxylic acid units) and alcohol units (polyol units, polyhydroxy compound units). In this invention, a polycarboxylic acid unit refers to a unit formed from a compound having multiple carboxyl groups. Additionally, a polyol unit or polyhydroxy compound unit refers to a unit formed from a compound having multiple hydroxyl groups. In this specification and claims, each acid and alcohol may also contain derivatives thereof. For example, an acid may also contain derivatives of the acid (e.g., esters).
[0085] As the first and second polyester resins, residues generated during film production and / or molding processes can be used. This enables efficient resource utilization and cost reduction in manufacturing. The residues can be processed into easily usable shapes such as granules and / or flakes, powders, etc.
[0086] In addition, the first and second polyester resins may contain components derived from recycled polyester resins or derived from biomass.
[0087] <First Polyester Resin>
[0088] The first polyester resin comprises a first acid unit and a first alcohol unit. The first polyester resin is preferably composed of polyethylene terephthalate (PET) as the main component.
[0089] The first acid unit mainly comprises terephthalic acid units. The content of terephthalic acid units relative to the total amount of the first acid unit is 90 mol% or more, preferably 95 mol% or more. For example, the content of terephthalic acid units relative to the total amount of acid units can be 100 mol%. If the content of terephthalic acid units is less than 90 mol%, it may sometimes impair the low adsorption capacity of organic compounds in the packaged product. For example, the content of terephthalic acid units relative to the total amount of the first acid unit can be 98 mol% or less, or 95 mol% or less.
[0090] The first acid unit may contain other acid units without altering the essential properties of the first polyester resin. Examples of other acid units include those formed from isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, succinic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, or derivatives thereof. One type may be used alone, or two or more may be used in combination.
[0091] The primary alcohol unit mainly comprises ethylene glycol units. The content of ethylene glycol units relative to the total amount of primary alcohol units can be, for example, 50 mol% or more, 55 mol% or more, 60 mol% or more, 62 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more. The content of ethylene glycol units relative to the total amount of primary alcohol units can be, for example, less than 95 mol%, less than 90 mol%, less than 85 mol%, less than 80 mol%, less than 75 mol%, less than 70 mol%, or less than 60 mol%.
[0092] The first alcohol unit further comprises a 2,2-dimethyl-1,3-propanediol unit (hereinafter sometimes also referred to as a "neopentyl glycol unit"). The content of the neopentyl glycol unit relative to the total amount of the first alcohol unit is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more. The content of the neopentyl glycol unit relative to the total amount of the first alcohol unit may, for example, be 20 mol% or more, 25 mol% or more, 30 mol% or more, or 35 mol% or more.
[0093] When the content of neopentyl glycol units is less than 5 mol%, the stability of heat sealing decreases. The content of neopentyl glycol units relative to the total amount of the first alcohol unit is 40 mol% or less, preferably 38 mol% or less, and more preferably 35 mol% or less. The content of neopentyl glycol units relative to the total amount of the first alcohol unit can be, for example, 30 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, or 10 mol% or less. When the content of neopentyl glycol units exceeds 40 mol%, the adsorption of organic compounds in the packaged product becomes significantly higher.
[0094] The total content of ethylene glycol units and neopentyl glycol units relative to the total amount of the first alcohol unit is preferably 90 mol% or more, more preferably 95 mol% or more. The total content of ethylene glycol units and neopentyl glycol units relative to the total amount of the first alcohol unit can be 100 mol%.
[0095] The first alcohol unit comprises a diethylene glycol unit. The content of the diethylene glycol unit relative to the total amount of the first alcohol unit is 0.1 mol% to 5 mol, preferably 0.5 mol% to 5 mol, more preferably 1 mol% to 5 mol, further preferably 1 mol% to 3 mol, and particularly preferably 1 mol% to 2 mol.
[0096] The presence of diethylene glycol units at a rate of 0.1 mol% or higher implies that the first alcohol unit necessarily contains diethylene glycol units.
[0097] When the content of diethylene glycol units exceeds 5 mol%, the heat resistance deteriorates. When storing the film or products containing the film in high-temperature environments such as summer, the film may fuse together, sometimes making it impossible to unwind in rolls or maintain the shape of the packaging.
[0098] Diethylene glycol is a byproduct of ethylene glycol during the melt polymerization of the first polyester resin, but additional diethylene glycol may be added as needed.
[0099] The first alcohol unit may contain other alcohol units without altering the essential properties of the first polyester resin. Examples of other alcohol units include those formed from 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediethanol, or derivatives thereof. One of these units may be used alone, or two or more may be used in combination.
[0100] The first polyester resin may further include crosslinking agent units. Examples of crosslinking agent units include tricarboxylic acid units or polyol units.
[0101] As a tricarboxylic acid unit, trimellitic acid units can be cited as an example. By including a crosslinking agent unit, the melt viscosity of the first polyester resin can be increased. As a result, the amount of polyester resin ejected during the formation of the polyester film is stable, and it is easy to form a polyester film of uniform thickness.
[0102] The content of trimellitic acid units relative to the total amount of the first acid unit can be, for example, 0.05 mol% or more, 0.1 mol% or more, or 0.15 mol% or more. The content of trimellitic acid units relative to the total amount of the first acid component is preferably 5 mol% or less. The content of trimellitic acid units relative to the total amount of the first acid unit can be, for example, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1 mol% or less, or 0.5 mol% or less. When the content of trimellitic acid units exceeds 5 mol%, the polyester film is prone to breakage.
[0103] The total content of terephthalic acid units and trimellitic acid units relative to the total amount of acid units is preferably 90 mol% or more, more preferably 95 mol% or more. The total content of terephthalic acid units and trimellitic acid units relative to the total amount of acid units can be set to 100 mol%.
[0104] The polyester film of the first and second embodiments preferably contains a second polyester resin or an anti-blocking agent in addition to the first polyester resin.
[0105] <Second Polyester Resin>
[0106] The second polyester resin comprises a second acid unit and a second alcohol unit.
[0107] The second polyester resin is preferably polyethylene terephthalate (PET) as the main structural unit.
[0108] The second acid unit mainly comprises terephthalic acid units. The content of terephthalic acid units relative to the total amount of the second acid unit is preferably 80 mol% or more, more preferably 85 mol% or more. The content of terephthalic acid units relative to the total amount of the second acid unit can be, for example, set to 90 mol% or more, 95 mol% or less, 90 mol% or less, or 85 mol% or less.
[0109] The second acid unit may further comprise isophthalic acid units. The content of isophthalic acid units relative to the total amount of the second acid unit is preferably 5 mol% or more, more preferably 10 mol% or more. The content of isophthalic acid units relative to the total amount of the second acid unit may, for example, be 15 mol% or more. The content of isophthalic acid units relative to the total amount of the second acid component may, for example, be 20 mol% or less, 15 mol% or less, or 10 mol% or less.
[0110] The total content of terephthalic acid units and isophthalic acid units relative to the total amount of the second acid unit is preferably 90 mol% or more, more preferably 95 mol% or more. The total content of terephthalic acid units and isophthalic acid units relative to the total amount of the second acid unit can be set to 100 mol%.
[0111] The second acid unit may contain other acid units without altering the essential properties of the second polyester resin. Examples of other acid units include those formed from phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, succinic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, trimellitic acid, or derivatives thereof. One type may be used alone, or two or more may be used in combination.
[0112] The second alcohol unit mainly comprises ethylene glycol units. The content of ethylene glycol units relative to the total amount of the second alcohol units is preferably 65 mol% or more, preferably 70 mol% or more. For example, the content of ethylene glycol units relative to the total amount of the second alcohol units can be set to 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. When the content of ethylene glycol units is less than 65 mol%, it may sometimes impair the low adsorption capacity for organic compounds in the packaged product. For example, the content of ethylene glycol units relative to the total amount of the second alcohol units can be set to 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less.
[0113] The second alcohol unit may contain other alcohol units without altering the essential properties of the second polyester resin. Examples of other alcohol units include those formed from neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediethanol, or derivatives thereof. These units may be used individually or in combination of two or more.
[0114] <Manufacturing Method of Polyester Resin>
[0115] The first and second polyester resins can be manufactured using known methods based on the aforementioned monomers and additives. For example, the ester prepolymer can be generated by direct esterification of an unsubstituted polycarboxylic acid as a starting material, or by transesterification of an esterified compound such as a dimethyl ester as a starting material. From the viewpoint of production efficiency, direct esterification is preferred.
[0116] The addition rates of monomers and additives can be set to the ratios shown in the above description relating to the first polyester resin and the second polyester resin.
[0117] Direct esterification or transesterification reactions can be carried out, for example, as follows: Raw materials are added to a reaction vessel equipped with a heating device, a stirrer, and a distillation tube; a reaction catalyst is added; and the reaction is carried out under an inert gas atmosphere at atmospheric pressure, with stirring and heating occurring simultaneously, while distilling to remove byproducts such as methanol generated during the reaction. The reaction temperature is preferably, for example, 150°C to 270°C, more preferably 160°C to 260°C. The reaction time is, for example, approximately 3 to 7 hours.
[0118] At least one metal compound can be used as a catalyst for the transesterification reaction. Examples of metal elements include sodium, potassium, calcium, titanium, lithium, magnesium, manganese, zinc, tin, and cobalt. Among these, titanium and manganese compounds are particularly preferred because they exhibit high reactivity and produce resins with good color. The amount of transesterification catalyst added relative to the resulting polyester resin is typically preferred to be 5 ppm to 1,000 ppm, and more preferably 10 ppm to 100 ppm.
[0119] To suppress the formation of diethylene glycol as a byproduct, it is preferable to reduce the amount of ethylene glycol in the reaction system. For example, the molar ratio of alcohol to acid (alcohol / acid) is preferably 1.3 or less. Alternatively, for example, 5 ppm of sodium hydroxide can be added to suppress the formation of diethylene glycol.
[0120] Furthermore, it is preferable to add a phosphorus compound after the direct esterification reaction or transesterification reaction to further carry out the esterification reaction. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, and tributyl phosphite. Among these, trimethyl phosphate is particularly preferred. The amount of phosphorus compound used relative to the mass of the generated polyester resin is preferably 5 ppm to 1,000 ppm, more preferably 20 ppm to 100 ppm.
[0121] In this invention, neopentyl glycol can be added during the direct esterification reaction of the polycarboxylic acid component and ethylene glycol, or it can be added after the esterification reaction is complete. Pre-mixing the polycarboxylic acid component with ethylene glycol and neopentyl glycol at room temperature to prepare a slurry before conducting the esterification reaction in the esterification tank can suppress the dispersion of neopentyl glycol, and is therefore preferred. Furthermore, in this invention, ethylene glycol can be added entirely before the esterification reaction, without the need to add a portion afterward.
[0122] Following the transesterification and esterification reactions, a polymerization catalyst can be added to the ester prepolymer to further induce a polycondensation reaction until the desired molecular weight is achieved. Germanium dioxide can be used as a catalyst in the polymerization reaction, for example. The catalyst addition rate can be set to 180 ppm to 220 ppm relative to the amount of resin produced. For example, after adding the polymerization catalyst, the polycondensation reaction can be carried out while gradually increasing the temperature and reducing the pressure in the reaction tank. The pressure in the tank is preferably ultimately 0.4 kPa or less, and more preferably reduced to 0.2 kPa or less. The temperature in the tank is preferably ultimately increased to 250°C to 290°C. For example, the polymerization reaction can be carried out under reduced pressure of 150 Pa or less in the tank until the desired melt viscosity is achieved. Then, the pressure in the tank is increased to, for example, 0.5 MPa, allowing the reaction product to be extruded from the bottom of the tank and recovered. For example, the reaction product can be extruded into a filament in water, cooled, and cut to obtain granular polyester resin.
[0123] Catalysts other than germanium dioxide can also be used as polymerization catalysts. For example, titanium dioxide can be used as a polymerization catalyst. When using titanium dioxide, the catalyst addition rate can be set to, for example, 1 ppm to 10 ppm relative to the amount of resin produced.
[0124] Anti-adhesion agent
[0125] Anti-blocking (slip agent) is formulated to improve the sliding properties between films.
[0126] As an anti-blocking agent, organic or inorganic microparticles can be used, such as inorganic particles like calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, lithium fluoride, alumina, silica, talc, and kaolin; organic particles like acrylic resins and guanidine resins; and precipitated particles formed by granulating catalyst residues. They can be used individually or in combination of two or more. Silica and talc are preferred.
[0127] The content of the anti-blocking agent relative to the total amount of the polyester film is preferably 0.05% to 1% by mass, more preferably 0.1% to 1% by mass. When the content of the anti-blocking agent is less than 0.05% by mass, sufficient film slippage may not be obtained.
[0128] It should be noted that the resin composition containing the second polyester resin and the antiblocking agent can be used, for example, as a masterbatch for adding an antiblocking agent to a polyester film.
[0129] <Other Ingredients>
[0130] In the polyester film of the present invention, various additives such as antioxidants, heat stabilizers, lubricants, antistatic agents, plasticizers, ultraviolet absorbers, and pigments can be appropriately blended according to the application and forming purpose. These additives can be blended in any step of the polymerization reaction process or the processing / forming process.
[0131] Examples of antioxidants include hindered phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, with hindered phenolic antioxidants being particularly preferred. The preferred addition amount is 100 ppm to 5,000 ppm. Furthermore, in the case of forming melt-extruded films, metal salts such as magnesium acetate, calcium acetate, and magnesium chloride can be added to stabilize the electrostatic adhesion of the cooling rollers.
[0132] <Manufacturing Method of Polyester Film>
[0133] There are no particular limitations on the method for manufacturing the polyester film of the present invention, and appropriate selections can be made according to the purpose. For example, the first polyester resin, the second polyester resin as needed, and other components can be mixed and fed into an extruder equipped with a T-die, melted, extruded using the T-die, and then sealed to a cooling roller by electrostatic sealing or other methods to cool and solidify it, thereby producing a polyester film (unstretched material). In this case, the temperature of the extruder is preferably 250°C to 280°C.
[0134] In the polyester film of the present invention, features other than those described above are sometimes difficult or impractical to determine directly from the composition. In such cases, the polyester film of the present invention should be determined by its manufacturing method. For example, the composition and properties of the polyester film sometimes depend on the heating and melting conditions during the production of the polyester film, and the polyester resin changes from before forming. Sometimes it is difficult to directly determine the composition and properties of the molded body; in such cases, it is useful to determine the polyester film by the manufacturing method from the polyester resin before forming to the polyester film.
[0135] The polyester film of the present invention can be a single-layer structure consisting of only one layer, or a laminated structure consisting of multiple films. In the case of a laminated structure, it is preferably 2 to 5 layers, more preferably 2 or 3 layers.
[0136] At least one of the multiple layers needs to contain the first polyester resin in the polyester film of the first embodiment or the second embodiment, and preferably all layers contain the first polyester resin.
[0137] The polyester film of the present invention can be, for example, a two-layer structure having a first layer and a second layer.
[0138] The first layer contains: a first polyester resin comprising 80% or more of a first polyester resin relative to the mass of the first layer and a second polyester resin comprising less than 20% of a second polyester resin relative to the mass of the first layer. The content of the first polyester resin is 80% or more of a first polyester resin relative to the mass of the first layer, preferably 85% or more of a first polyester resin, more preferably 90% or more of a first polyester resin, even more preferably 93% or more of a first polyester resin, even more preferably 96% or more of a first polyester resin, particularly preferably 98% or more of a first polyester resin, and may also be 100% by mass.
[0139] The second layer contains a first polyester resin at a mass percentage of 90% or more relative to the mass of the second layer. The content of the first polyester resin relative to the mass of the second layer is preferably 95% or more, but may also be 100% by mass.
[0140] The first layer preferably also contains an anti-blocking agent at a mass percentage of 0.05% to 1% relative to the first layer.
[0141] The total thickness of the two-layer polyester film is preferably 25μm to 100μm, more preferably 25μm to 90μm, even more preferably 25μm to 80μm, even more preferably 30μm to 80μm, particularly preferably 30μm to 70μm, even more particularly preferably 30μm to 60μm, and even more particularly preferably 30μm to 50μm.
[0142] The polyester film of the present invention may, for example, be a three-layer structure having a third layer between the first layer and the second layer.
[0143] The first and second layers are the same as the first and second layers of the two-layer structure described above.
[0144] The third layer contains: the first polyester resin, which accounts for more than 80% by mass relative to the third layer, and the second polyester resin, which accounts for less than 20% by mass relative to the third layer.
[0145] The content of the first polyester resin relative to the mass of the third layer is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 93% by mass or more, even more preferably 96% by mass or more, particularly preferably 98% by mass or more, and may also be 100% by mass.
[0146] The third layer preferably also contains an anti-blocking agent at a mass percentage of 0.05% to 1% relative to the third layer.
[0147] The total thickness of the three-layer polyester film is preferably 25μm to 100μm, more preferably 25μm to 90μm, even more preferably 25μm to 80μm, even more preferably 30μm to 80μm, particularly preferably 30μm to 70μm, even more particularly preferably 30μm to 60μm, and even more particularly preferably 30μm to 50μm.
[0148] Hereinafter, the polyester film of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, reference numerals are used for understanding the invention and are not intended to limit the scope of the illustrations. Furthermore, the shapes, sizes, scales, etc., of the illustrations are not limited to those shown in the drawings. In each embodiment, the same reference numerals are used to denote the same elements.
[0149] Figure 1 An example of the polyester film of the present invention with a single-layer structure. Figure 1 The polyester film 1 is composed of a first layer 2. The composition of the first layer 2 may be the same as that of the polyester film in the first embodiment or the second embodiment.
[0150] The thickness of the first layer 2 (the thickness of the single-layer polyester film 1) is preferably 25μm to 100μm, more preferably 25μm to 90μm, even more preferably 25μm to 80μm, even more preferably 30μm to 80μm, particularly preferably 30μm to 70μm, even more particularly preferably 30μm to 60μm, and even more particularly preferably 30μm to 50μm.
[0151] Figure 2 An example of the polyester film of the present invention with a two-layer structure. Figure 2 The polyester film 10 has a first layer 11 and a second layer 12 laminated on the first layer 11.
[0152] The composition of the first layer 11 can be the same as that of the first polyester resin in the polyester film of the present invention.
[0153] The combined thickness of the first layer 11 and the second layer 12 (the thickness of the polyester film 10 with a two-layer structure) is preferably 25 μm to 100 μm, more preferably 25 μm to 90 μm, even more preferably 25 μm to 80 μm, even more preferably 30 μm to 80 μm, particularly preferably 30 μm to 70 μm, even more preferably 30 μm to 60 μm, and even more preferably 30 μm to 50 μm.
[0154] The first layer 11 can be a heat-sealing layer. The first layer 11 has a thickness of 5 μm or more, preferably 10 μm or more. If the first layer 11 is less than 5 μm, sufficient heat-sealing strength and low adsorption may not be obtained. The first layer 11 may, for example, have a thickness of 20 μm or less, 15 μm or less, or 10 μm or less.
[0155] The composition of the second layer 12 can be the same as that of the second polyester resin in the polyester film of the present invention.
[0156] The second layer 12 has a thickness of 5 μm or more, preferably 10 μm or more. If the thickness of the second layer 12 is less than 5 μm, sufficient heat-sealing strength and low adsorption may not be obtained. The second layer 12 may, for example, have a thickness of 20 μm or less, 15 μm or less, or 10 μm or less.
[0157] Figure 3 An example of the polyester film of the present invention with a three-layer structure. Figure 3 The polyester film 20 has a first layer 21, a second layer 22 laminated on the first layer 21, and a third layer 23 laminated on the second layer 22.
[0158] The composition of the first layer 21 can be the same as that of the first polyester resin in the polyester film of the present invention.
[0159] The total thickness of the first layer 21, the second layer 22, and the third layer 23 (the thickness of the polyester film 20 with a three-layer structure) is preferably 25 μm to 100 μm, more preferably 25 μm to 90 μm, even more preferably 25 μm to 80 μm, even more preferably 30 μm to 80 μm, particularly preferably 30 μm to 70 μm, even more preferably 30 μm to 60 μm, and even more preferably 30 μm to 50 μm.
[0160] The first layer 21 can be a heat-sealing layer. The first layer 21 has a thickness of 5 μm or more, preferably 10 μm or more. If the first layer 21 is less than 5 μm, sufficient heat-sealing strength and low adsorption may not be obtained. The first layer 21 may, for example, have a thickness of 20 μm or less, 15 μm or less, or 10 μm or less.
[0161] The composition of the second layer 22 can be the same as that of the second polyester resin in the polyester film of the present invention.
[0162] The second layer 22 has a thickness of 5 μm or more, preferably 10 μm or more. If the second layer 22 is less than 5 μm, sufficient heat-sealing strength and low adsorption may not be obtained. The second layer 22 may, for example, have a thickness of 20 μm or less, 15 μm or less, or 10 μm or less.
[0163] The composition of the third layer 23 can be the same as that of the first polyester resin in the polyester film of the present invention.
[0164] The third layer 23 has a thickness of 5 μm or more, preferably 10 μm or more. If the thickness of the third layer 23 is less than 5 μm, sufficient heat-sealing strength and low adsorption may not be obtained. The third layer 23 may, for example, have a thickness of 20 μm or less, 15 μm or less, or 10 μm or less.
[0165] The polyester film of the present invention exhibits low adsorption of organic compounds in the packaged material and achieves high sealing strength, excellent tearability and shapeability, thus enabling it to be widely used in various applications, and is particularly suitable for use in laminates, packaging bodies, food and beverage packaging bodies, cosmetic packaging bodies, pharmaceutical / quasi-pharmaceutical packaging bodies and products as described below.
[0166] (Layered structure)
[0167] The laminate of the present invention has a substrate film and a sealing layer, and further may have other layers as needed. The above-described laminate is suitable for packaging applications.
[0168] <Sealing layer>
[0169] The polyester film of the present invention is used as a sealing layer. The sealing layer is disposed on the outermost surface of the laminate, and may be disposed on one or both sides of the substrate film.
[0170] <Substrate Film>
[0171] As a substrate film, there are no particular restrictions on the material, thickness, or structure; it can be selected appropriately according to the purpose. Regarding structure, examples include single-layer structures and multi-layer structures.
[0172] Materials used as substrates include, for example, polyester resin, polyolefin resin, polyamide resin, polyurethane resin, fluoropolymer resin, polystyrene resin, poly(meth)acrylic acid resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), vinyl alcohol resin, halogenated resin (polyvinyl chloride resin, etc.), polyphenylene ether resin, polycarbonate resin, polyimide resin, polyamide-imide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, acetal resin, cellulose resin, etc.
[0173] The thickness of the substrate is preferably 1μm to 100μm, more preferably 5μm to 50μm.
[0174] <Other Layers>
[0175] Other layers include, for example, metal layers, adhesive layers, primer layers, resin layers, etc.
[0176] Examples of metal layers include aluminum foil and aluminum vapor-deposited thin films.
[0177] (Packaging)
[0178] The packaging body of the present invention comprises the polyester film of the present invention, at least a portion of which is fused together. Examples of packaging bodies include food and beverage packaging bodies, cosmetic packaging bodies, or pharmaceutical / quasi-pharmaceutical packaging bodies.
[0179] -Food and beverage packaging-
[0180] The food and beverage packaging of the present invention comprises the polyester film of the present invention and the food and beverage covered by the polyester film.
[0181] Depending on the intended use, food and beverage packaging may consist of only a portion of the packaging material (the polyester film of this invention), or it may consist substantially entirely of the packaging material.
[0182] Examples of packaging forms for food and beverages include bags, trays, pouches, soft bags, and containers.
[0183] Food and beverage packaging is used to package various food and beverage products. In this invention, "food and beverage product" is not particularly limited, but can include, for example, beverages such as soft drinks, carbonated drinks, nutritional drinks, fruit drinks, and lactic acid drinks (including concentrated stock solutions and powders for preparation); frozen desserts such as ice cream, shaved ice, and shaved ice; noodles such as buckwheat noodles, udon noodles, rice noodles, dumpling wrappers, shumai wrappers, Chinese noodles, and instant noodles; snacks such as maltose, chewing gum, candy, chewing gum, chocolate, compressed candy, snacks, biscuits, jelly, jam, cream, and baked goods; processed aquatic / livestock products such as fish cakes, ham, and sausages; dairy products such as processed milk and fermented milk; oils and oil-processed foods such as fish and shellfish, salad oil, tempura oil, margarine, mayonnaise, shortening, whipped cream, and sauces; seasonings such as sauces and condiments; soups, stews, salads, side dishes, and pickled vegetables; other forms of health / nutritional supplements; and beverage preparations.
[0184] -Cosmetic Packaging-
[0185] The cosmetic packaging of the present invention comprises the polyester film of the present invention and the cosmetic product covered by the polyester film.
[0186] Depending on the intended use, cosmetic packaging may consist of only a portion of the packaging material (the polyester film of this invention), or it may consist entirely of the packaging material.
[0187] Examples of cosmetic packaging forms include bags, trays, pouches, and containers.
[0188] Cosmetic packaging is used to package various cosmetics. In this invention, "cosmetic" is not particularly limited, and examples include perfumes, creams, lotions, toners, serums, face masks, foundations, lipsticks, hair conditioners, hair lotions, shampoos, hair treatments, and hair conditioning agents.
[0189] -Pharmaceutical / quasi-pharmaceutical packaging-
[0190] The pharmaceutical / quasi-pharmaceutical packaging of the present invention comprises the polyester film of the present invention and the pharmaceutical / quasi-pharmaceutical covered by the polyester film.
[0191] Depending on the intended use, the pharmaceutical / quasi-pharmaceutical packaging may consist of only a portion of the packaging material (the polyester film of the present invention), or it may consist substantially entirely of the packaging material.
[0192] Examples of packaging forms for pharmaceuticals / quasi-pharmaceuticals include blister packs, bags, trays, pouches, and containers.
[0193] Pharmaceutical / quasi-pharmaceutical packaging is used to package various pharmaceuticals / quasi-pharmaceuticals. In this invention, pharmaceuticals / quasi-pharmaceuticals refer to pharmaceuticals and quasi-pharmaceuticals as defined in Article 2, Paragraph 1 and Paragraph 2 of the Japanese Pharmaceutical Machinery Law. These can be dosage forms for oral administration, such as liquids, suspensions, tablets, capsules, powders, etc., or dosage forms for non-oral administration, such as ointments, patches, poultices, dental cleaning agents, mouthwashes, oral cooling agents, gels, ointments, mouthwash tablets, sprays, aerosols, etc.
[0194] (product)
[0195] The product of the present invention comprises: a package containing an organic compound, and a polyester film of the present invention for packaging the package, wherein at least a portion of the polyester film is fused together with each other.
[0196] The product of the present invention comprises: a packaged item (contents) containing an organic compound, and at least one polyester film selected from the polyester film of the first embodiment and the polyester film of the second embodiment, wherein the polyester film packages the packaged item.
[0197] In the products of this invention, at least a portion of the polyester film is fused together, particularly by heat fusion. The products of this invention have a packaged item (contents) containing an organic compound and a packaging body that holds the packaged item. The packaged item is preferably completely surrounded (sealed) by the polyester film.
[0198] The product according to the present invention can inhibit the adsorption of organic compounds onto polyester film. Therefore, the quality of the packaged item can be maintained.
[0199] The organic compound may be selected from at least one of the following groups: limonene, camphor, menthol, methyl salicylate, tocopheryl acetate, isopropyl methylphenol, ketoprofen, ketoprofen sodium, diclofenac sodium, biphenylacetic acid, loxoprofen sodium, tobuterol, rivastigmine, chlorpromazine hydrochloride, haloperidol, risperidone, paliperidone, buspirone, perropirone hydrochloride hydrate, lurasidone hydrochloride, olanzapine, quetiapine fumarate, cloxapine maleate, clozapine, aripiprazole, and buripiperazole.
[0200] Limonene can be used, for example, as a flavoring agent for citrus fruits. Examples of packaging materials containing limonene as an organic compound include hair care cosmetics and skin care cosmetics.
[0201] Camphor can be used as a blood circulation improver, anti-inflammatory agent, and analgesic. Examples of packaging materials containing camphor as an organic compound include pharmaceuticals / quasi-pharmaceuticals such as patches.
[0202] Menthol can be used as a fragrance, flavoring agent, and odorant. Examples of packaging materials containing menthol as an organic compound include pharmaceutical patches, quasi-pharmaceuticals, dental cleaning agents, cosmetics, beverages, and food products such as snacks.
[0203] Methyl salicylate can be used as an analgesic, anti-inflammatory agent, etc. Examples of pharmaceutical / quasi-pharmaceutical products containing methyl salicylate as an organic compound include patches.
[0204] Tocopheryl acetate can be used, for example, as a treatment for vitamin E deficiency and a blood circulation enhancer. Examples of pharmaceutical / quasi-pharmaceutical products containing tocopheryl acetate as an organic compound include patches.
[0205] Isopropyl methylphenol can be used, for example, as a bactericide. Examples of packaging materials containing isopropyl methylphenol as an organic compound include topical skin treatments such as ointments and cosmetics.
[0206] Ketoprofen, ketoprofen sodium, and loxoprofen sodium can be used as, for example, anti-inflammatory agents, analgesics, and antipyretics. Examples of pharmaceutical / quasi-pharmaceutical products containing ketoprofen, ketoprofen sodium, or loxoprofen sodium as organic compounds include, for instance, patches.
[0207] Diclofenac sodium and biphenylacetic acid can be used, for example, as anti-inflammatory agents, analgesics, etc. Examples of pharmaceutical / quasi-pharmaceutical products containing diclofenac sodium or biphenylacetic acid as organic compounds include patches.
[0208] Tobacterol can be used, for example, as a bronchodilator. Examples of pharmaceutical / quasi-pharmaceutical products containing tobacterol as an organic compound include patches.
[0209] Rosavirin can be used, for example, as a treatment for Alzheimer's disease. Examples of pharmaceutical / quasi-pharmaceutical products containing rivasavirin as an organic compound include patches.
[0210] Chlorpromazine hydrochloride and haloperidol can be used, for example, as antipsychotic agents. Examples of pharmaceutical products containing chlorpromazine hydrochloride or haloperidol as organic compounds include antipsychotic agents.
[0211] Risperidone, paliperidone, buprofen, piperoprone hydrochloride hydrate, and lurasidone hydrochloride can be used, for example, as SDAs (serotonin-dopamine antagonists). Examples of pharmaceutical products containing risperidone, paliperidone, buprofen, piperoprone hydrochloride hydrate, or lurasidone hydrochloride as organic compounds include antipsychotic drugs.
[0212] Olanzapine, quetiapine fumarate, cloxapine maleate, and clozapine can be used, for example, as MARTA (an antipsychotic that acts on multiple receptors). Examples of pharmaceutical products that include olanzapine, quetiapine fumarate, or clozapine as organic compounds include antipsychotic medications.
[0213] Aripiprazole and bripiprazole can be used, for example, as DPA / DSS (partial dopamine agonists). Examples of pharmaceutical products containing aripiprazole or bripiprazole as organic compounds include antipsychotic drugs.
[0214] Example
[0215] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments in any way.
[0216] (Synthesis Example 1 of Polyester Resin 1)
[0217] In a stainless steel (registered trademark) autoclave equipped with a stirrer and a distillation column, 99.8 mol% terephthalic acid, 0.2 mol% trimellitic anhydride, 70 mol% ethylene glycol, and 30 mol% neopentyl glycol were added. Esterification was carried out at 250°C and 250 kPa. Then, triethyl phosphate and germanium dioxide were added, and polycondensation was carried out at 275°C and 100 Pa under reduced pressure until the specified viscosity was reached. The mixture was extruded into cooling water and granulated using a wire cutter. Thus, polyester resin 1 (hereinafter, sometimes referred to as "resin 1") was synthesized.
[0218] The intrinsic viscosity (IV) of the obtained resin 1 is 0.83 dl / g.
[0219] Intrinsic viscosity
[0220] 0.5000±0.0005g of polyester resin was dissolved in a mixed solvent of phenol:tetrachloroethane = 60:40 (mass ratio), and the intrinsic viscosity (IV) of the polyester resin at 20°C was measured using an automatic viscometer (manufactured by Sun Electronic Industries, Ltd., AVL-6C).
[0221] (Synthesis Examples 2-7 of Polyester Resins 2-7)
[0222] In Example 1 of the synthesis of polyester resin 1, the types and amounts of monomers in the feed composition shown in Table 1 were changed. Otherwise, polyester resins 2 to 7 (hereinafter sometimes referred to as "resins 2 to 7") were synthesized in the same manner as in Example 1 of the synthesis of resin 1. It should be noted that polyester resin 8 (resin 8) is a commercially available product.
[0223] Next, for each of the obtained polyester resins, the following procedure was performed to determine the resin composition using NMR. The results of the resin composition are shown together with the molar composition of the monomers in Table 1.
[0224] <Composition of Polyester Resin>
[0225] Using an FT-NMR apparatus (DPX400, manufactured by Bruker BioSpin), polyester resin was dissolved in deuterated chloroform, and tetramethylsilane was mixed as a standard. The proton NMR spectrum was measured, and the type and content of each unit were calculated based on the obtained NMR spectrum.
[0226] [Table 1]
[0227]
[0228] The following abbreviations are used in Table 1.
[0229] TPA: Terephthalic acid
[0230] IPA: Isophthalic acid
[0231] TMA: Trimericic Acid
[0232] EG: Ethylene glycol
[0233] NPG: Neopentyl glycol (2,2-dimethyl-1,3-propanediol)
[0234] CHDM: 1,4-Cyclohexanediethanol
[0235] DEG: Diethylene glycol
[0236] (Experimental Examples 1-29)
[0237] Using polyester resins 1 to 8 shown in Table 1 (resin 8 is a commercially available product) and L-LDPE (linear low-density polyethylene) which is a commercially available product, polyester films as shown in Tables 2-1 to 2-5 are produced as follows.
[0238] [Thin Film Fabrication]
[0239] Using a T-die, polyester films of Test Examples 1 to 27 (Tables 2-1 to 2-5) were produced by co-extrusion at a forming temperature of 280°C. The films of Test Examples 28 and 29 were commercially available products.
[0240] In Experiments 1-17 and 21-27, the resulting melt was fed into a T-die, formed into a sheet from the nozzle, and extruded. It was then cooled and solidified on a casting roller to obtain polyester films (unstretched) with the thicknesses shown in Tables 2-1 to 2-5. The tensile elongation of the obtained polyester films was all above 200%.
[0241] For Example 18, a polyester film prepared in the same manner as in Example 5 was uniaxially stretched at a length (MD) ratio of 3.5 times at a temperature of 90°C to obtain a polyester film with a thickness of 30 μm.
[0242] For Example 19, a polyester film prepared in the same manner as in Example 13 was uniaxially stretched at a ratio of 3.5 times along the MD direction at a temperature of 90°C to obtain a polyester film with a thickness of 30 μm.
[0243] For Example 20, a polyester film prepared in the same manner as in Example 13 was biaxially stretched at 80°C along the MD direction at a ratio of 3 times and at 95°C along the width (TD) direction at a ratio of 3 times, and then heat-set at 180°C to obtain a polyester film with a thickness of 30 μm.
[0244] For the polyester films obtained from each test example, each characteristic was evaluated as follows. The results are shown in Tables 2-1 to 2-5. The content of the first polyester resin in the polyester films in Tables 2-1 to 2-5 is the content of the first polyester resin specified in claim 1, specifically, it refers to the content of polyester resin 1, polyester resin 2, or polyester resin 3 in Table 1 equivalent to the first polyester resin.
[0245] <Sealing strength>
[0246] Two polyester films, 1 and 2, were prepared from the polyester films of each test example. The first layer of the two polyester films 1 and 2 were overlapped, and a heat sealer (Tester Sangyo Co., Ltd., TP-701-B HEAT SEAL TESTER) was used to heat seal the films at 130°C, 140°C, and 150°C for 2 seconds at a pressure of 0.2 MPa to form a laminate. Next, 15 mm wide strips of test pieces were cut from the laminates. The sealing strength of the test pieces was measured by tensile testing machine (Minebea Co., Ltd., TECHNO GRAPH TG-5kN) at a tensile speed of 100 mm / min, and evaluated according to the following criteria.
[0247] [Evaluation Criteria]
[0248] A: Sealing strength is 15N / 15mm or higher.
[0249] B: Sealing strength less than 15N / 15mm
[0250] <Adsorption Test>
[0251] The initial mass A of test pieces (4cm x 4cm squares) obtained by cutting polyester films from each test example was determined. The test piece was placed at the bottom of a beaker with the sealing layer (first layer) on the top side, and 5 ml of limonene (manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.) was added. The beaker was then covered with aluminum foil and stored at 25°C for 7 days. After 7 days, the test piece was removed, the limonene adhering to its surface was wiped off, and the mass of the test piece was measured. The adsorption capacity of limonene was calculated from the difference between the initial mass A and the mass B after 7 days (BA). The adsorption capacity of limonene was evaluated according to the following criteria.
[0252] [Evaluation Criteria]
[0253] A: The adsorption capacity of limonene is 0.2 mg / cm³. 2 the following
[0254] B: The adsorption capacity of limonene exceeds 0.2 mg / cm³. 2
[0255] <Enthalpy of fusion (ΔHm)>
[0256] The enthalpy of fusion (ΔHm) was determined by integrating the endothermic peak at 220°C to 260°C when the test pieces obtained by cutting 10 mg of polyester film from each test example were heated from 25°C to 300°C at a heating rate of 10°C / min.
[0257] <Tear strength>
[0258] The tear test was performed based on the trouser tear method of JIS K7128-1 (1998).
[0259] For each test piece, the polyester film was cut into strips with a long side of 150 mm and a short side of 50 mm. A 75 mm long slit was made in the center of the short side, parallel to the long side. Tensile tests were performed using a tensile testing machine (Minebea Co., Ltd., TECHNO GRAPH TG-5kN) at 23°C and a speed of 200 mm / min along both the length (MD) and width (TD) directions. The tear strength was calculated by dividing the average tear load at 20 mm, 30 mm, 40 mm, 50 mm, 60 mm, and 70 mm from the point of tearing by the thickness of the test piece.
[0260] <Elastic Modulus>
[0261] For the test pieces obtained by cutting the polyester film of each test example into strips with a long side of 100 mm and a short side of 10 mm, a tensile testing machine (Minebea Co., Ltd., TECHNO GRAPH TG-5kN) was used to conduct tensile tests in the length (MD) and width (TD) directions at 50 mm / min in an environment of 23°C. The elastic modulus in the length (MD) and width (TD) directions was measured and the average value was calculated.
[0262] <Heat Shrinkage Rate>
[0263] The polyester film from each test example was cut into squares with 200 mm sides to obtain test pieces. The test pieces were placed in a forced-air drying oven heated to 90°C and left to stand for 3 minutes. The length (MD) and width (TD) directions (A) of the test pieces were measured before standing. After 3 minutes, the test pieces were removed from the forced-air drying oven, and the length (MD) and width (TD) directions (B) of the test pieces were measured. The heat shrinkage rate (%) was calculated from the measured lengths A and B as follows: [(AB) / A] × 100.
[0264] [Table 2-1]
[0265]
[0266] [Table 2-2]
[0267]
[0268] [Table 2-3]
[0269]
[0270] *1: The tear occurred at an angle, therefore it could not be determined.
[0271] [Table 2-4]
[0272]
[0273] [Table 2-5]
[0274]
[0275] *Resin 8: Commercially available product (polyester resin)
[0276] *L-LDPE: Commercially available product (linear low-density polyethylene)
[0277] It should be noted that in Experimental Examples 1 to 29 of Tables 2-1 to 2-5, limonene was used as a representative organic compound to evaluate adsorption properties. However, the same level of adsorption properties can also be obtained by using camphor, menthol, methyl salicylate, tocopheryl acetate, isopropyl methylphenol, ketoprofen, ketoprofen sodium, diclofenac sodium, biphenylacetic acid, loxoprofen sodium, tobuterol, rivastigmine, chlorpromazine hydrochloride, haloperidol, risperidone, paliperidone, buspirone, piperoprin hydrochloride hydrate, lurasidone hydrochloride, olanzapine, quetiapine fumarate, cloxapine maleate, clozapine, aripiprazole, or buripiperazole.
[0278] As can be seen from the results in Tables 2-1 to 2-5, Test Examples 1 to 12, 18, 22 to 23 and 25 to 26 meet all the conditions (A) to (C) below. Therefore, a polyester film with low adsorption to organic compounds in the packaged item and high sealing strength, a package containing the polyester film, and a product containing the above-mentioned polyester film can be obtained.
[0279] (A) The polyester film contains: a first polyester resin comprising a first acid unit and a first alcohol unit, the first acid unit comprising terephthalic acid units comprising 90 mol% or more of the total amount of the first acid unit, the first alcohol unit comprising ethylene glycol units comprising 50 mol% or more of the total amount of the first alcohol unit, 2,2-dimethyl-1,3-propanediol units comprising 5 mol% to 40 mol% of the total amount of the first alcohol unit, and diethylene glycol units comprising 0.1 mol% to 5 mol% of the total amount of the first alcohol unit.
[0280] (B) The content of the first polyester resin is 80% or more by mass relative to the total amount of polyester film.
[0281] (C) The thickness of the polyester film is 25μm~100μm.
[0282] In addition, it is expected that the polyester film of the present invention will have low adsorption of organic compounds in the packaged items, high sealing strength, and excellent tearability and shapeability.
[0283] Therefore, it is preferable to satisfy all of the conditions (A) to (C) above, and further to satisfy at least one of the conditions (D) to (J) below, and it is particularly preferable to satisfy all of the conditions (A) to (J).
[0284] (D) In the differential scanning calorimetry (DSC) measurement of polyester film, the enthalpy of fusion (ΔHm) calculated by integrating the endothermic peak at 220℃~260℃ when the temperature is increased from 25℃ to 300℃ at a heating rate of 10℃ / min is less than 10J / g.
[0285] (E) The tear strength of the polyester film obtained by tensile testing at 23°C and 200 mm / min is 2 N / mm to 15 N / mm in both the length and width directions.
[0286] (F) The elastic modulus of the polyester film, determined by tensile testing at 23°C and 50 mm / min, is 1.6 kN / mm in both the length and width directions. 2 ~2.2kN / mm 2 .
[0287] (G) The heat shrinkage rate of the polyester film before and after heat treatment in hot air at 90°C for 3 minutes is less than 10% in both the length and width directions.
[0288] (H) When two polyester films 1 and 2 are heat-pressed together at 130℃~150℃, 0.2MPa and 2 seconds, the sealing strength between polyester film 1 and polyester film 2 is 15N / 15mm~50N / 15mm.
[0289] (I) The initial mass of test pieces obtained by cutting polyester film into 4cm×4cm squares was determined. The test pieces were added to a beaker, followed by 5ml of limonene. The beaker was then covered and stored at 25℃ for 7 days. The mass of the test pieces was then measured. The difference between the initial mass A and the mass B after 7 days (BA) represents the adsorption capacity of limonene, which is 0.2mg / cm³. 2 the following.
[0290] (J) The polyester film is an unstretched material.
[0291] Test Examples 1-12, 22-23 and 25-26 satisfy all the conditions (A)-(J) above. Therefore, it can be seen that they have low adsorption of organic compounds in the packaged items, high sealing strength, and excellent low adsorption and tearability.
[0292] Experimental Example 13 does not meet the conditions (A), (D) and (E) above. Therefore, the result is that the melting enthalpy (ΔHm) becomes higher and the tearability is poor.
[0293] Test Examples 14, 15 and 17 do not meet the conditions (A), (D) and (E) above. The polyester film does not contain 2,2-dimethyl-1,3-propanediol units, and the melting enthalpy (ΔHm) is high, resulting in poor tearability.
[0294] Experimental Example 16 does not meet the conditions (A) and (I) above. The content of 2,2-dimethyl-1,3-propanediol units is high, so the adsorption of limonene is high, resulting in poor adsorption of organic compounds in the packaged product.
[0295] Test Example 18 does not meet the conditions (D), (E), (F), (G) and (J) above. Extending along the MD direction, the elastic modulus, tear strength and thermal shrinkage rate in the MD direction become higher, thus resulting in poor shapeability.
[0296] Test Example 19 does not meet the conditions (A), (D), (E), (F), (G), and (J) above. Extending along the MD direction, the elastic modulus, tear strength, and thermal shrinkage rate in the MD direction increase, resulting in poor shapeability. In addition, due to the high enthalpy of fusion (ΔHm), it results in poor tearability by hand.
[0297] Test Example 20 does not meet the conditions (A), (D), (F), and (J) above. It extends in both the MD and TD directions, resulting in a higher elastic modulus and thus poor shapeability. In addition, due to the high enthalpy of fusion (ΔHm), it also results in poor tearability.
[0298] Test Example 21 did not meet the conditions (C) and (H) above. The polyester film was thin, resulting in poor sealing strength.
[0299] Test Example 24 does not meet the conditions (C) and (I) above. The polyester film is thick, so the adsorption of limonene is greater, resulting in poor adsorption of organic compounds in the packaged product.
[0300] Test Example 27 does not meet the conditions (A) and (I) above. The content of the first polyester resin is low, so the adsorption of limonene is increased, resulting in poor adsorption of organic compounds in the packaged product.
[0301] Test Example 28 did not meet the conditions (A), (G), and (I) above, resulting in a higher heat shrinkage rate and thus poor shapeability. Furthermore, because the polyester film contained 1,4-cyclohexanediethanol units instead of 2,2-dimethyl-1,3-propanediol units, the adsorption of limonene increased, resulting in poor adsorption of organic compounds in the packaged material.
[0302] Test Example 29 did not meet the conditions (A), (D), (E), (F), (H), and (I) above, and used commercially available linear low-density polyethylene (L-LDPE), resulting in poor shapeability and tearability. Furthermore, it resulted in increased adsorption of limonene and poor adsorption of organic compounds in the packaged material.
[0303] Industrial availability
[0304] The polyester film of the present invention has low adsorption of organic compounds in the packaged contents and high sealing strength, preferably with excellent tear-resistance and shapeability. Therefore, it is widely used in laminates and various packaging materials, and is particularly suitable for use in food and beverage packaging, cosmetic packaging, and pharmaceutical / quasi-pharmaceutical packaging.
[0305] Explanation of reference numerals in the attached figures
[0306] 1. Polyester film
[0307] 2. First floor
[0308] 10 Polyester film
[0309] 11. Level 1
[0310] 12 Second Floor
[0311] 20 Polyester film
[0312] 21. First floor
[0313] 22 Second Floor
[0314] 23. The third floor.
Claims
1. A polyester film, characterized in that, It contains: a first polyester resin comprising a first acid unit and a first alcohol unit, The first acid unit comprises terephthalic acid units at a total percentage of 90 mol% or more relative to the total amount of the first acid unit. The first alcohol unit comprises ethylene glycol units in an amount of 50 mol% or more relative to the total amount of the first alcohol unit, 2,2-dimethyl-1,3-propanediol units in an amount of 5 mol% to 40 mol% and diethylene glycol units in an amount of 0.1 mol% to 5 mol%. The content of the first polyester resin is 80% or more by mass relative to the total amount of the polyester film. The thickness of the polyester film is 25μm to 100μm.
2. The polyester film according to claim 1, wherein, In the differential scanning calorimetry (DSC) measurement of the polyester film, the enthalpy of fusion ΔHm calculated by integrating the endothermic peak at 220°C to 260°C when the temperature is increased from 25°C to 300°C at a heating rate of 10°C / min is less than 10 J / g.
3. The polyester film according to claim 1, wherein, The tear strength of the polyester film, determined by tensile testing at 23°C and 200 mm / min, ranged from 2 N / mm to 15 N / mm in both the length and width directions.
4. The polyester film according to claim 1, wherein, The elastic modulus of the polyester film, determined by tensile testing at 23°C and 50 mm / min, is 1.6 kN / mm in both the length and width directions. 2 ~2.2kN / mm 2 .
5. The polyester film according to claim 1, wherein, The thermal shrinkage rate of the polyester film before and after heat treatment in hot air at 90°C for 3 minutes is less than 10% in both the length and width directions.
6. The polyester film according to claim 1, wherein, When two polyester films 1 and 2 are heat-pressed together at 130℃~150℃, 0.2MPa, and 2 seconds, the sealing strength between polyester film 1 and polyester film 2 is 15N / 15mm~50N / 15mm.
7. The polyester film according to claim 1, wherein, The initial mass of test pieces obtained by cutting the polyester film into 4cm × 4cm squares was determined. The test pieces were added to a beaker, along with 5ml of limonene. The beaker was then covered and stored at 25°C for 7 days. The mass of the test pieces was then measured. The difference between the initial mass A and the mass B after 7 days, BA, represents the adsorption capacity of limonene, which is 0.2mg / cm³. 2 the following.
8. The polyester film according to claim 1, wherein, The polyester film is an unstretched material.
9. The polyester film according to claim 1, wherein, The first polyester resin further includes a crosslinking agent unit.
10. The polyester film according to claim 1, wherein, The first acid unit further comprises trimellitic acid units in an amount of 0.05 mol% to 5 mol% relative to the total amount of the first acid unit.
11. The polyester film according to claim 1, further comprising 0.05% to 1% by mass of an anti-blocking agent.
12. The polyester film according to claim 1, comprising a first layer and a second layer, The first layer contains a first polyester resin comprising 80% or more of the first polyester resin relative to the first layer and a second polyester resin comprising less than 20% of the second polyester resin relative to the first layer. The second layer contains the first polyester resin at a mass percentage of 90% or more relative to the second layer.
13. The polyester film according to claim 12, wherein, The first layer also contains an anti-blocking agent at a mass percentage of 0.05% to 1% relative to the first layer.
14. The polyester film according to claim 12, further comprising a third layer between the first layer and the second layer. The third layer comprises: a first polyester resin comprising 80% or more of the mass of the third layer, and a second polyester resin comprising less than 20% of the mass of the third layer.
15. The polyester film according to claim 14, wherein, The third layer also contains an anti-blocking agent at a mass percentage of 0.05% to 1% relative to the mass of the third layer.
16. A laminate having a substrate film and a sealing layer, The sealing layer comprises the polyester film according to any one of claims 1 to 15.
17. A packaging body comprising the polyester film according to any one of claims 1 to 15, At least a portion of the polyester film is fused together with each other.
18. A food and beverage packaging body, characterized in that, A polyester film having any one of claims 1 to 15 and a food or beverage covered by said polyester film.
19. A cosmetic packaging body, characterized in that, A polyester film having any one of claims 1 to 15 and a cosmetic product covered by said polyester film.
20. A pharmaceutical / quasi-pharmaceutical packaging body, characterized in that, A polyester film having any one of claims 1 to 15 and a pharmaceutical / quasi-pharmaceutical covered by said polyester film.
21. A product comprising: a packaging containing an organic compound, and a polyester film for packaging the packaging according to any one of claims 1 to 15. At least a portion of the polyester film is fused together with each other.
22. The product according to claim 21, wherein, The organic compound is selected from at least one of the following groups: limonene, camphor, menthol, methyl salicylate, tocopheryl acetate, isopropyl methylphenol, ketoprofen, ketoprofen sodium, diclofenac sodium, biphenylacetic acid, loxoprofen sodium, tobuterol, rivastigmine, chlorpromazine hydrochloride, haloperidol, risperidone, paliperidone, buspirone, perropirone hydrochloride hydrate, lurasidone hydrochloride, olanzapine, quetiapine fumarate, cloxapine maleate, clozapine, aripiprazole, and buripiperazole.
Citation Information
Patent Citations
Packaging pouch for accommodating adhesive preparation and package for adhesive preparation
JP2005328928A