WO2017057506A1 - ポリエステル系ラベルおよび包装容器 - Google Patents
ポリエステル系ラベルおよび包装容器 Download PDFInfo
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- WO2017057506A1 WO2017057506A1 PCT/JP2016/078707 JP2016078707W WO2017057506A1 WO 2017057506 A1 WO2017057506 A1 WO 2017057506A1 JP 2016078707 W JP2016078707 W JP 2016078707W WO 2017057506 A1 WO2017057506 A1 WO 2017057506A1
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/58—Cuttability
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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
- B32B2307/736—Shrinkable
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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
- B32B2307/746—Slipping, anti-blocking, low friction
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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
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/60—Bottles
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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
- B32B2439/40—Closed containers
- B32B2439/62—Boxes, cartons, cases
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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
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
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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
- B32B2519/00—Labels, badges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2203/00—Decoration means, markings, information elements, contents indicators
- B65D2203/02—Labels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a polyester label after a heat-shrinkable polyester film is thermally shrunk and a packaging container on which the label is coated.
- polyester-based heat that has high heat resistance, easy incineration, and excellent solvent resistance for uses such as label packaging, cap seals, and integrated packaging that protect glass bottles or plastic bottles and display products.
- Shrinkable films have been widely used as shrinkage labels, and the amount of use tends to increase with an increase in PET (polyethylene terephthalate) bottle container beverages and the like.
- a heat-shrinkable film having a thickness of 40 to 60 ⁇ m has been used as a heat-shrinkable label for covering PET bottles (for example, Patent Document 1).
- the heat-shrinkable film used for packaging becomes just garbage after using the contents. Therefore, in response to growing environmental awareness to reduce dust as much as possible, film manufacturers are also considering reducing the thickness of heat-shrinkable polyester films.
- the thickness of the heat-shrinkable label is reduced, naturally the thickness of the label after heat-shrinkage (hereinafter simply referred to as the label after heat-shrink) is also reduced, so that the label was covered during truck transportation.
- General heat-shrinkable film has high tensile breaking strength in the main shrinking direction, but low tensile breaking strength in the direction perpendicular to the shrinking direction. It was easy for cracks to occur due to this contact.
- JP 2003-12831 A Japanese Patent No. 5240387
- an object of the present invention is to provide a label with a low occurrence frequency of cracks, even if the label is a film using a thin film and a relatively low strength.
- the present invention that has solved the above problems is a polyester-based label characterized by satisfying the following requirements (1) to (6).
- the thickness of the base film of the label is 8 ⁇ m or more and 30 ⁇ m or less.
- the intrinsic viscosity of the polyester constituting the label is 0.58 dl / g or more.
- the label is orthogonal to the main shrinkage direction and the main shrinkage direction.
- the ratio of absorbance in the main contraction direction of the label The difference between (1340 cm ⁇ 1 / 1410 cm ⁇ 1 ) and the absorbance ratio (1340 cm ⁇ 1 / 1410 cm ⁇ 1 ) in the direction orthogonal to the main shrinkage direction of the label is 0.2 or more.
- Group constituting the label The specific heat capacity difference ⁇ Cp before and after Tg when the reversible heat capacity curve is measured with a temperature-modulated differential scanning calorimeter for the material film is 0.2 J / (g ⁇ ° C.) or more.
- the present invention includes a packaging container having the label on at least a part of the outer periphery of the container.
- the label of the present invention was able to respond to the demand for thinning and to suppress the occurrence of cracks during transportation.
- the label of the present invention is a heat-shrinkable polyester film coated with a tubular heat-shrinkable polyester label formed by overlapping both ends of a heat-shrinkable polyester film and adhering with an organic solvent. It is a label after shrinkage.
- the end means an end in the width direction (direction along the longitudinal direction).
- the heat-shrinkable polyester film is not only a film comprising only one polyester layer, but also a film having a laminated structure (may be five or more layers) such as a resin / polyester other than polyester / polyester, and both outer layers are made of polyester. Also included are laminated films.
- the polyester used for the heat-shrinkable polyester film is preferably composed mainly of an ethylene terephthalate unit. It is because it is excellent in strength and heat resistance.
- the ethylene terephthalate unit is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more, in 100 mol% of the polyester structural unit.
- dicarboxylic acid components constituting the polyester include aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. And an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid.
- the polyester does not contain a trivalent or higher polyvalent carboxylic acid (for example, trimellitic acid, pyromellitic acid, and anhydrides thereof).
- a trivalent or higher polyvalent carboxylic acid for example, trimellitic acid, pyromellitic acid, and anhydrides thereof.
- the diol component constituting the polyester includes ethylene glycol, 1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-n-butyl-2-ethyl-1,3-propanediol.
- Aliphatic diols such as 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 1,4-butanediol, hexanediol, neopentyl glycol, Examples thereof include alicyclic diols such as 1,4-cyclohexanedimethanol and aromatic diols such as bisphenol A.
- alicyclic diols such as 1,4-cyclohexanedimethanol and diols having 3 to 6 carbon atoms (for example, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, hexane) It is preferable to use a diol or the like.
- 1,3-propanediol it is easy to obtain a polyester that satisfies the requirements (1) to (6), which are essential requirements of the present invention.
- 1,3-propanediol is preferably used for the following reason.
- the thermal shrinkage rate in the longitudinal direction usually increases, leading to problems such as vertical shrinkage.
- vertical sinking means that the edge of the label that has been heat-shrinked by covering the bottle is curved (for example, curved downward at the upper edge and curved upward at the lower edge), resulting in a poor appearance. is there. That is, it means a phenomenon in which the length of the bottle in the vertical direction (height direction) is shortened.
- the polyester constituting the label preferably has 5 mol% or more and 15 mol% or less of units derived from propanediol in 100 mol% of the units constituting the polyester.
- the amount is less than 5 mol%, the heat shrinkage rate in the longitudinal direction is increased, and when the bottle is covered and heat-shrinked, problems such as vertical shrinkage are caused, which is not preferable.
- it is 6 mol% or more, More preferably, it is 8 mol% or more, Most preferably, it is 10 mol% or more.
- the upper limit of the unit derived from propanediol is not particularly limited, but if the number of units derived from propanediol is increased, the raw material cost becomes high, and about 15 mol% is preferable.
- the total of at least one monomer component that can be an amorphous component in 100 mol% of the polyhydric alcohol component or 100 mol% of the polyvalent carboxylic acid component in all polyester resins is preferably 17 mol% or more. Is at least 18 mol%, more preferably at least 19 mol%, particularly preferably at least 20 mol%.
- the upper limit of the total amount of monomer components that can be amorphous components is not particularly limited, but is preferably 30 mol%.
- Examples of the monomer that can be an amorphous component include neopentyl glycol, 1,4-cyclohexanedimethanol, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,2-diethyl-1 , 3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3- Examples thereof include propanediol and hexanediol. Among these, neopentyl glycol, 1,4-cyclohexanedimethanol or isophthalic acid is preferably used.
- the polyester should not contain a diol having 8 or more carbon atoms (for example, octanediol) or a trihydric or higher polyhydric alcohol (for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.). Is preferred. With heat-shrinkable polyester-based labels obtained by using polyesters containing these diols or polyhydric alcohols, it is difficult to achieve the necessary high shrinkage rate. Further, it is also preferable that the polyester does not contain diethylene glycol, triethylene glycol, or polyethylene glycol as much as possible.
- various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents are used as necessary.
- An agent, a heat stabilizer, a coloring pigment, a coloring inhibitor, an ultraviolet absorber, and the like can be added.
- fine particles as a lubricant for improving the workability (slidability) of the film.
- the fine particles any one can be selected.
- inorganic fine particles silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, etc.
- organic fine particles for example, acrylic resin Examples thereof include particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles.
- the average particle size of the fine particles is in the range of 0.05 to 3.0 ⁇ m (when measured with a Coulter counter) and can be appropriately selected as necessary.
- the fine particles into the resin forming the heat-shrinkable polyester film for example, it can be added at any stage of producing the polyester resin, but it can be added at the esterification stage or transesterification reaction. After completion, it is preferable to add as a slurry dispersed in ethylene glycol or the like at a stage before the start of the polycondensation reaction, and proceed with the polycondensation reaction.
- a method of blending a slurry of fine particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester resin material, or a dried fine particle and a polyester resin material using a kneading extruder It is also preferable to carry out by a method of blending and the like.
- the above heat-shrinkable polyester film can be subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the adhesion of the film surface.
- the heat-shrinkable polyester film includes a laminated polyester film having at least one polyester resin layer.
- the polyester resin layer may be a polyester having the same composition or a polyester having a different composition.
- the layer that can be laminated as a layer other than polyester is not particularly limited as long as it is a thermoplastic resin layer, but is preferably a polystyrene-based resin layer from the viewpoint of cost and heat shrinkage characteristics.
- the other layers may be one layer or two or more layers.
- polystyrene resins include homopolymers and copolymers of styrene derivatives such as styrene, ⁇ -methylstyrene and p-methylstyrene, as well as monomers copolymerizable with styrene and styrene derivatives such as acrylic acid, Copolymerization with methacrylic acid, metal salts thereof (for example, metal salts such as Na, K, Li, Mg, Ca, Zn, and Fe), aliphatic unsaturated carboxylic acids such as acrylates and methacrylates, and derivatives thereof
- a block copolymer with a polymer or butadiene can also be used.
- polystyrene, styrene-butyl acrylate copolymer, styrene-butadiene block copolymer and the like are preferable.
- thermoplastic resin examples include polystyrene having atactic structure, styrene resins such as AS resin and ABS resin, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, nylon 6, nylon 66, nylon 12 and nylon 4. And polyamide resins such as polyhexamethylene adipamide, and polyolefin resins such as polyethylene, polypropylene, and polybutene.
- a rubbery copolymer containing a styrene compound as a constituent component is preferable, and examples thereof include a random, block or graft copolymer obtained by copolymerizing one or more of styrene and a rubber component.
- examples of such rubbery copolymer include styrene-butadiene copolymer rubber, styrene-isoprene block copolymer, rubber obtained by hydrogenating a part or all of the butadiene portion, and methyl acrylate-butadiene-styrene.
- Examples include copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber, and methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber.
- the rubbery copolymer containing the above-mentioned styrene compound as a constituent component has a styrene unit, and therefore has good dispersibility with respect to a polystyrene resin having a syndiotactic structure, and has an effect of improving plasticity with respect to the polystyrene resin. large.
- the rubber-like copolymer which contains the above-mentioned styrene-type compound as the structural component can be used conveniently.
- rubber components include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber, urethane rubber, silicone rubber, acrylic rubber, polyether-ester rubber, polyester-ester rubber. Etc. can be used.
- the weight average molecular weight of the polystyrene-based resin is preferably 10,000 or more, and more preferably 50,000 or more. Those having a weight average molecular weight of less than 10,000 are not preferred because the strength retention and heat resistance of the film are liable to decrease.
- the upper limit of the weight average molecular weight is not particularly limited, but if it exceeds 1,500,000, it is not preferable because breakage or the like accompanying an increase in stretching tension may occur.
- Various types of polystyrene resins are commercially available from various manufacturers, and commercially available resins may be used.
- the label of the present invention is a heat-shrinkable polyester film thermally contracted.
- heat shrinking heat shrinking is usually performed in a state where a heat shrinkable label (label before heat shrinking) is attached to the bottle.
- the thickness of the base film of the label is 8 ⁇ m or more and 30 ⁇ m or less. Since the present invention is intended for thinned labels, the thickness must be in this range.
- the thickness of the base film of the label is more preferably 9 ⁇ m or more and 28 ⁇ m or less, further preferably 10 ⁇ m or more and 26 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the intrinsic viscosity of the polyester constituting the label of the present invention is 0.58 dl / g or more. If the intrinsic viscosity of the label is 0.58 dl / g or more, the tensile elongation at break of the label also increases and the frequency of occurrence of cracks decreases. More preferably, it is 0.60 dl / g or more, More preferably, it is 0.61 dl / g or more. A higher intrinsic viscosity is preferable, but if it is too high, the load on the raw material extrusion machine or the like during film production increases, so 0.9 dl / g is the upper limit.
- the tensile breaking elongation of the label of the present invention is 5% or more in both the main shrinkage direction and the direction orthogonal to the main shrinkage direction.
- the tensile breaking elongation in the main shrinkage direction of the label is more preferably 15% or more, and further preferably 25% or more.
- Higher tensile rupture elongation is preferred, but considering that it is more susceptible to solvent attack when manufacturing heat-shrinkable labels, and that characteristics tend to change when heat-shrinkable labels are stored for long periods of time. 50% is the upper limit.
- the label of the present invention is a label after heat shrinkage, it still has a margin for heat shrinkage.
- the direction contracted at this time is the main contraction direction.
- the tensile elongation at break in the direction perpendicular to the main shrinkage direction of the label is more preferably 6% or more, and even more preferably 7% or more.
- the upper limit is approximately 20% for the same reason as described above.
- the label of the invention when calculated absorbance at 1340 cm -1 and 1410 cm -1 in the polarization ATR method for the base film constituting the label, the label main shrinking direction of the absorbance ratio (1340cm -1 / 1410cm -1), the difference between the direction of the absorbance ratio perpendicular to the main shrinkage direction of a label (1340cm -1 / 1410cm -1) is 0.2 or more. If this difference is less than 0.2, the complicated production method described in Patent Document 2 must be carried out in order to suppress the appearance defects such as vertical sink. The difference is more preferably 0.22 or more, and further preferably 0.24 or more.
- the absorbance ratio represents a trans conformation ratio of molecular orientation.
- the trans conformation is considered to represent the entangled state of the molecular chain, and the entangled state of the molecular chain is high when the trans conformation ratio is high. Therefore, a small difference between the absorbance ratio in the main contraction direction and the absorbance ratio in the direction orthogonal to the main contraction direction means that the contraction rate in the longitudinal direction is close to the contraction rate in the width direction.
- the polarization ATR method is a method for analyzing the molecular orientation of the sample surface (about several ⁇ m). Therefore, in the laminated polyester film, the absorbance ratio in the outermost polyester layer is the above numerical value. The method for measuring the absorbance ratio will be described later.
- the base film which comprises a label is the meaning except a layer other than a printing layer and other heat-shrinkable films.
- the label of the present invention has a specific heat capacity difference ⁇ Cp (corresponding to a movable amorphous amount) before and after Tg of 0.2 J / when a reversible heat capacity curve is measured with a temperature-modulated differential scanning calorimeter for the base film constituting the label. (G ⁇ ° C) or more.
- a reversible heat capacity curve is measured with a temperature modulation differential scanning calorimeter for the label sample, the baseline shifts at a temperature corresponding to Tg.
- the difference between the values before and after the shift is referred to as the specific heat capacity difference ⁇ Cp, which corresponds to the movable amorphous amount.
- the movable amorphous is an amorphous where the molecular chain starts to move in the vicinity of Tg, and can be distinguished from a rigid amorphous where the molecular chain cannot move unless the temperature is higher than Tg.
- the inventors have found that the amount of movable amorphous material affects the heat shrinkage rate. In order to obtain a film that has a high heat shrinkage rate and is difficult to shrink in the longitudinal direction, it is important not to change the movable amorphous to a rigid amorphous or to change most of the rigid amorphous to a movable amorphous.
- ⁇ Cp is less than 0.2 J / (g ⁇ ° C.)
- the amount of movable amorphous material is small, so that it is easily affected by a solvent attack when forming a heat-shrinkable label. It is thought that the label is greatly deteriorated by long-term storage. If the deterioration is large, the label after heat shrinkage becomes brittle, and cracks are likely to occur.
- ⁇ Cp is more preferably 0.23 J / (g ⁇ ° C.) or more, and further preferably 0.26 J / (g ⁇ ° C.) or more.
- the upper limit is not particularly limited from the above viewpoint, but is generally about 0.6 J / (g ⁇ ° C.) in consideration of an increase in the natural shrinkage rate of the base film constituting the heat-shrinkable label.
- the difference between the maximum value and the minimum value in the vertical direction (height direction) of the label is 3 mm or less.
- the length of the label is the length in the vertical direction if the label is in a state of covering the bottle. If the vertical mark is caused, the difference between the maximum value and the minimum value in the vertical direction of the label may exceed 3 mm, which means that an appearance defect has occurred. Therefore, in the label of the present invention, the difference between the maximum value and the minimum value of the length in the vertical direction is set to 3 mm or less.
- the difference between the maximum value and the minimum value of the vertical length of the label is preferably 2 mm or less, and more preferably 1 mm or less.
- the tensile breaking strength in the direction orthogonal to the main shrinkage direction is preferably 5 MPa or more and 60 MPa or less. If it is less than 5 MPa, cracks are likely to occur due to insufficient strength of the label. 7 MPa or more is more preferable, and 9 MPa or more is more preferable. Higher tensile rupture strength is preferable, but 60 MPa is the upper limit because the complicated production method described in Patent Document 2 must be carried out.
- the heat-shrinkable polyester film used in the present invention is formed by melting and extruding the above-described polyester raw material with an extruder to form an unstretched film, and stretching and heat-treating the unstretched film by a predetermined method shown below. Can be obtained. When laminating, a plurality of extruders, feed blocks, and multi-manifolds may be used.
- the polyester can be obtained by polycondensing the above-described preferred dicarboxylic acid component and diol component by a known method. Usually, two or more kinds of chip-like polyester are mixed and used as a raw material for the film.
- the raw material chips are dried using a dryer such as a hopper dryer or paddle dryer, or a vacuum dryer, and extruded into a film at a temperature of 200 to 280 ° C.
- a dryer such as a hopper dryer or paddle dryer, or a vacuum dryer
- an undried polyester raw material is similarly extruded into a film while removing moisture in a vented extruder.
- any existing method such as T-die method or tubular method may be adopted.
- the temperature at the time of extrusion should not exceed 280 ° C. If the melting temperature is too high, the intrinsic viscosity at the time of labeling is lowered and cracks are likely to occur, which is not preferable.
- the molten resin is quenched to obtain an unstretched film.
- the “unstretched film” includes a film on which a tension necessary for film feeding is applied.
- a method of rapidly cooling the molten resin a method of obtaining a substantially unoriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly solidifying it can be suitably employed.
- ⁇ Stretching is performed on this unstretched film.
- the stretching treatment may be performed continuously after cooling with the above-described casting roll or the like, or may be wound once in the form of a roll after cooling and then performed.
- the main shrinkage direction is the film transverse (width) direction
- an example of a stretching method when the main shrinkage direction is the transverse direction is shown below.
- the film can be stretched according to ordinary operations such as changing the stretching direction by 90 ° in the following method.
- the unstretched film obtained above is heated with a roll at 70 to 100 ° C., preferably 80 to 90 ° C., if necessary, and then the speed difference of the roll is used within a range of 1.1 to 1.8 times.
- the obtained film after longitudinal stretching is preheated at 80 to 120 ° C., preferably 90 to 110 ° C. if necessary, and then 3.0 times or more by a tenter or the like in the transverse direction (direction perpendicular to the extrusion direction) Preferably, it is stretched 3.5 times or more and 7 times or less.
- the stretching temperature is 65 ° C. or higher and 100 ° C. or lower, preferably 70 ° C. or higher and 95 ° C. or lower.
- the heat treatment is performed to relieve the tension state of the stretched film, and is effective in adjusting the heat shrinkage rate at the temperature during the heat treatment and reducing the natural shrinkage rate.
- the heat treatment there is a problem that when the stretched film is heated in the heat treatment zone, the bowing phenomenon occurs and the physical properties in the width direction are deteriorated (reference: molding processing, 4 (5), 312 (1992)). Thereby, the heat-shrinkable polyester film used as the label of the present invention is obtained.
- the heat-shrinkable polyester film can be used as a heat-shrinkable label by a known method. Specifically, a heat-shrinkable polyester film cut to a desired width is subjected to appropriate printing, and the left and right ends of the film are overlapped and joined by solvent adhesion or the like to produce a tube film. This tube film is cut into an appropriate length to obtain a tube-shaped label.
- organic solvent for adhesion cyclic ethers such as 1,3-dioxolane or tetrahydrofuran are preferable.
- aromatic hydrocarbons such as benzene, toluene, xylene and trimethylbenzene
- halogenated hydrocarbons such as methylene chloride and chloroform
- phenols such as phenol, and mixtures thereof
- a perforated tunnel (steam tunnel) of the type in which perforations are formed on the label by a known method and then covered with a PET bottle, the PET bottle is placed on a belt conveyor or the like, and steam is blown, or hot air is blown The inside of the shrinking tunnel (hot air tunnel).
- the labels pass through these tunnels, the labels are thermally contracted, so that the labels after the thermal contraction are attached to a bottle container such as a PET bottle.
- the label of the present invention is a label after this heat shrinkage.
- packaging objects include PET bottles for beverages, various bottles, cans, plastic containers such as confectionery and lunch boxes, and paper boxes.
- the label is heat-shrinked by about 5 to 70% and adhered to the package.
- the label that is to be covered with the packaging object may be printed or may not be printed.
- the packaging container which has the label of this invention in at least one part of the outer periphery of a container is also contained in this invention.
- the measuring method of the physical property of the film and label obtained by the Example and the comparative example is as follows.
- Heat shrinkage hot water heat shrinkage
- the heat-shrinkable polyester film is cut into a 10 cm x 10 cm square along the longitudinal direction and its orthogonal direction (width direction) and immersed in warm water at 90 ° C ⁇ 0.5 ° C for 10 seconds under no load.
- the sample was immediately immersed in water at 25 ° C. ⁇ 0.5 ° C. for 10 seconds and then pulled out from the water, and the lengths in the vertical and horizontal directions of the sample were measured.
- Thermal shrinkage rate (%) ⁇ (length before shrinkage ⁇ length after shrinkage) / length before shrinkage ⁇
- the direction with the largest shrinkage rate (main shrinkage direction) of the film is the width direction.
- the inflection point was determined using the attached analysis software (TA Instruments; TA Analysis), and the heat capacity difference before and after the inflection point (glass transition point; Tg) was determined according to the following formula.
- the heat capacity difference ⁇ Cp (J / (g ⁇ ° C.)) was used.
- the above-mentioned inflection point refers to a point where the value obtained by differentiating the reversible heat capacity curve twice when the reversible heat capacity curve is an ideal curve without irregularities is zero.
- Reversible heat capacity difference ⁇ Cp (J / (g ⁇ ° C.)) (Heat capacity on the higher temperature side than Tg) ⁇ (heat capacity on the lower temperature side than Tg)
- Tg-5 ° C. which is linearly fitted by the least square method, is used as the extension line of the base line of the heat capacity curve on the lower temperature side than Tg. Then, the intersection point with the tangent at the inflection point (Tg) is obtained, the value of the Y axis (reversible heat capacity) at this intersection point is read, the heat capacity on the low temperature side, and the difference between the heat capacity value on the high temperature side and the heat capacity on the low temperature side The heat capacity difference ⁇ Cp (J / (g ⁇ ° C.)) was used.
- the absorbance ratio (1340 cm ⁇ 1 / 1410 cm ⁇ 1 ) of 1340 cm ⁇ 1 and 1410 cm ⁇ 1 of the heat shrinkable polyester film or the label after heat shrinkage was determined by the polarized ATR method. Specifically, using an FT-IR apparatus (“FTS 60A / 896”, manufactured by Varian), the measurement wavelength region (650 to 4000 cm ⁇ 1 ) by the ATR method, the number of integrations is 128 times, and infrared is applied with polarized light. The absorption band of the absorption spectrum was used. From the obtained absorbance ratio, a difference was obtained according to the following formula, and was defined as a difference in absorbance ratio.
- Absorbance ratio difference Absorbance ratio in the main contraction direction of the label-Absorbance ratio in the direction perpendicular to the main contraction direction of the label
- ⁇ sp specific viscosity
- t0 solvent dropping time using Ostwald viscometer
- t tip (or label) solution dropping time using Ostwald viscometer
- C concentration of chip (or label) solution is there.
- a cylindrical heat-shrinkable label (a label in which the main shrinkage direction of the heat-shrinkable film is a circumferential direction) was produced by adhering both ends of the heat-shrinkable film with dioxolane. After that, cut in 210mm pitch in the longitudinal direction to make heat-shrinkable label, and label the 500ml square PET bottle (the body is a square with a cross section of 55mm on one side, the minimum part of the neck is a square with a cross section of 25mm on one side).
- the label was thermally shrunk by passing through a steam tunnel (model: SH-1500-L) manufactured by Fuji Astec Inc with a zone temperature of 80 ° C. in 2.5 seconds, and attached to the bottle. In addition, at the time of mounting, it adjusted so that the square part of 31 mm of one side might become the upper end of a label in a neck part.
- Chips A and C having the compositions shown in Table 1 were obtained in the same manner as in Synthesis Example 1.
- DEG is an abbreviation for diethylene glycol
- PD is 1,3-propanediol.
- SiO 2 Siliconicia 266 manufactured by Fuji Silysia
- Intrinsic viscosity was 0.75 dl / g for chip A and 0.92 dl / g for chip C.
- Table 2 shows commercially available polystyrene resins used in Example 5.
- “Clearen” is a registered trademark of Denki Kagaku Kogyo Co., Ltd.
- Tefprene is a registered trademark of Asahi Kasei Chemicals.
- Example 1 Method for producing heat-shrinkable film> Chip A, chip B and chip C described above were pre-dried separately, and as shown in Table 3, mixed at 20% by weight of chip A, 70% by weight of chip B and 10% by weight of chip C and put into an extruder.
- This mixed resin was melted at 260 ° C., extruded from a T-die, brought into contact with a rotating metal roll cooled to a surface temperature of 30 ° C., and quenched to obtain an unstretched film having a thickness of 121 ⁇ m.
- the take-up speed of the unstretched film was about 20 m / min.
- Tg of the unstretched film was 73 degreeC.
- the unstretched film was guided to a longitudinal stretching machine.
- the film was preheated on a preheating roll of a longitudinal stretching machine until the film surface temperature reached 85 ° C., and longitudinally stretched 1.5 times using a roll speed difference. After longitudinal stretching, it was cooled with a roll having a surface temperature of 30 ° C.
- the obtained film after longitudinal stretching was guided to a tenter (lateral stretching machine).
- the temperature of the preheating process was 100 ° C.
- the temperature of the stretching process was 75 ° C.
- the film was stretched 4.5 times in the width direction.
- the film after transverse stretching was heat-treated in a tension state at 88 ° C. for 8 seconds.
- Example 2 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 1 except that the melting temperature was increased to 280 ° C. The evaluation results are shown in Table 4. Although the intrinsic viscosity was slightly reduced by aging from the film, cracks were not generated and the film was a good label.
- Example 3 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 1 except that Chip A, Chip B, and Chip C were changed to a mass ratio of 30:60:10. The evaluation results are shown in Table 4. Although the specific heat capacity difference ⁇ Cp before and after Tg was decreased by aging from the film, cracks were not generated, and the film was a good label.
- Example 4 A 9 ⁇ m thick film was produced in the same manner as in Example 1 except that the thickness of the unstretched film was 60 ⁇ m. The evaluation results are shown in Table 4. There was no generation of cracks and the label was good.
- Example 5 Using a co-extrusion method, core layer forming resin, skin layer forming resin, and adhesive layer forming resin are melt-extruded from separate extruders (first to third extruders) and dies (T-die). By laminating inside and winding around a rotating metal roll cooled to 30 ° C. by air knife method and quenching, the thickness is 121 ⁇ m. Adhesive layer) was laminated, and unstretched films (polystyrene-based resin laminated sheets) having a structure in which skin layers were laminated on the outer sides of the intermediate layers were obtained. The method for forming each layer of the unstretched film (steps until melt extrusion) is as follows.
- the first layer, the second layer, the third layer, the fourth layer, and the fifth layer are referred to in order from the front side of the polystyrene-based resin laminated sheet (that is, the surface of the fifth layer is a metal roll). Contact surface).
- the take-up speed of the unstretched film was about 20 m / min.
- the pre-dried chip D is placed in a hopper directly above the second extruder. It supplied continuously with the fixed amount screw feeder. Then, the supplied chip D was melt-extruded from a T-die of a single-screw second extruder (melt-extruded so as to be laminated on the outer sides of the core layer). The temperature of the second extruder was adjusted to 200 ° C. Similarly to the extrusion by the first extruder, a helical type and parallel type gear pump was interposed between the extruder and the T die in order to stabilize the extrusion from the T die.
- the temperature of the third extruder was also adjusted to 200 ° C. Also, like the extrusion by the first extruder and the extrusion by the second extruder, in order to stabilize the extrusion from the T die, a helical type and parallel type gear pump was interposed between the extruder and the T die. .
- the discharge amount of the first to third extruders in the formation of the unstretched film is the thickness of the first layer / second layer / third layer / fourth layer / fifth layer. , 33/3/49/3/33 (total thickness 121 ⁇ m).
- the evaluation results are shown in Table 4. It was a good label with no cracks.
- Comparative Example 1 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 1 except that the melting temperature was raised to 310 ° C. The evaluation results are shown in Table 4. Since the film was aged, the tensile rupture elongation in the longitudinal direction, the intrinsic viscosity, and the specific heat capacity difference ⁇ Cp before and after Tg were lowered due to aging, and cracks were generated.
- Comparative Example 2 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 1 except that the mass ratio of the chip A and the chip B was changed to 30:70. The evaluation results are shown in Table 4. The shrinkage rate in the longitudinal direction of the film was high, and vertical marks were generated, resulting in an unsuitable label.
- Comparative Example 3 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 2 except that the mass ratio of chip A, chip B, and chip C was changed to 5:80:15. The evaluation results are shown in Table 4. As a result of aging, the intrinsic viscosity and the tensile elongation at break decreased, and cracks were generated, which was an inappropriate label.
- Comparative Example 4 A film having a thickness of 4 ⁇ m was produced in the same manner as in Example 2 except that the thickness of the unstretched film was 27 ⁇ m. Although the intrinsic viscosity was only slightly reduced by aging, the label was thin, so that cracks occurred and the label was unsuitable.
- Reference example 1 A film having a thickness of 40 ⁇ m was produced in the same manner as in Comparative Example 1 except that the thickness of the unstretched film was changed to 270 ⁇ m. The evaluation results are shown in Table 4. Although the intrinsic viscosity was lowered by aging, no crack was generated because the thickness of the label was thick.
- the label of the present invention is useful as a beverage bottle label and the like because it can meet the demand for thinning and can suppress the occurrence of cracks during transportation.
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Abstract
Description
上記課題を解決し得た本発明は、以下の(1)~(6)の要件を満足することを特徴とするポリエステル系ラベルである。
(1)ラベルの基材フィルムの厚みが8μm以上30μm以下
(2)ラベルを構成するポリエステルの極限粘度が0.58dl/g以上
(3)ラベルの主収縮方向および主収縮方向に対して直交する方向の引張破断伸度がいずれも5%以上
(4)ラベルを構成する基材フィルムについて偏光ATR法で1340cm-1の吸光度と1410cm-1の吸光度を求めた場合、ラベル主収縮方向の吸光度比(1340cm-1/1410cm-1)と、ラベルの主収縮方向に対して直交する方向の吸光度比(1340cm-1/1410cm-1)との差が0.2以上
(5)ラベルを構成する基材フィルムについて温度変調示差走査熱量計で可逆熱容量曲線を測定したときのTg前後の比熱容量差ΔCpが、0.2J/(g・℃)以上
(6)ラベルの鉛直方向の長さの最大値と最小値の差が3mm以下
ラベルの主収縮方向に対して直交する方向の引張破断強度は、5MPa以上60MPa以下であることが好ましい。
ラベルを構成するポリエステルが、ポリエステルを構成するユニット100モル%中、プロパンジオール由来のユニットを5モル%以上15モル%以下有することが好ましい。
本発明には、上記ラベルを容器の外周の少なくとも一部に有する包装容器も含まれる。
ポリスチレン系樹脂は、各種メーカーにより、種々のグレードのものが市販されており、市販のものを使用してもよい。
本発明のラベルは、ラベルを構成する基材フィルムについて温度変調示差走査熱量計で可逆熱容量曲線を測定したときのTg前後の比熱容量差ΔCp(可動非晶量に相当する)が0.2J/(g・℃)以上でなければならない。ラベル試料について、温度変調示差走査熱量計で可逆熱容量曲線を測定すると、Tgに相当する温度でベースラインがシフトする。シフト前後の値の差を比熱容量差ΔCpといい、これが可動非晶量に相当するとされている。可動非晶とは、Tg付近で分子鎖が動き出す非晶であり、Tgよりも高い温度にならなければ分子鎖が動ける状態とならない剛直非晶とは区別できる。この可動非晶の量が熱収縮率を左右することを本発明者らは見出している。そして、可動非晶を剛直非晶へと変化させないこと、あるいは剛直非晶の多くを可動非晶へ変化させることが、高熱収縮率で、長手方向に縮みにくいフィルムを得るために重要である。ΔCpが0.2J/(g・℃)よりも小さいと、可動非晶量が少ないため、熱収縮性ラベルにする際の溶剤アタックによる悪影響を受けやすく、また、熱収縮性ラベルにした後の長期保管によりラベルの劣化が大きいと考えられる。劣化が大きいと、熱収縮後のラベルが脆くなり、クラックが生じやすくなる。ΔCpは、0.23J/(g・℃)以上がより好ましく、0.26J/(g・℃)以上がさらに好ましい。なお、その上限は上記観点からは特に限定されないが、熱収縮性ラベルを構成する基材フィルムの自然収縮率の増大などを考慮すると、おおむね、0.6J/(g・℃)程度である。
熱収縮性ポリエステル系フィルムを長手方向およびその直交方向(幅方向)に沿うように10cm×10cmの正方形に裁断し、90℃±0.5℃の温水中に、無荷重状態で10秒間浸漬して熱収縮させた後、直ちに25℃±0.5℃の水中に10秒浸漬した後、水中から引き出して、試料の縦および横方向の長さを測定し、下記式に従って求めた値である。
熱収縮率(%)={(収縮前の長さ-収縮後の長さ)/収縮前の長さ}
本実施例では、フィルムの最も収縮率の大きい方向(主収縮方向)は幅方向である。
温度変調示差走査熱量計(DSC、「Q100」;TA Instruments社製)を用い、サンプルとして、熱収縮性ポリエステル系フィルム、または熱収縮後のラベルをハーメチックアルミニウムパン内に10.0±0.2mg精秤し、MDSC(登録商標)ヒートオンリーモードで、平均昇温速度1.0℃/min、変調周期40秒で測定し、可逆熱容量曲線を得た。得られた熱容量曲線において、付属の解析ソフト(TA Instruments社製;TA Analysis)を用いて変曲点を求め、変曲点(ガラス転移点;Tg)前後の熱容量差を下記式に従って求め、可逆熱容量差ΔCp(J/(g・℃))とした。ここで、上記の変曲点とは、可逆熱容量曲線が凹凸のない理想的な曲線である場合に、可逆熱容量曲線を2回微分したときの値が0である点をいう。
可逆熱容量差ΔCp(J/(g・℃))=(Tgよりも高温側の熱容量)-(Tgよりも低温側の熱容量)
吸光度比の差=ラベル主収縮方向の吸光度比-ラベル主収縮方向に対して直交する方向の吸光度比
[引張破断強度、伸度]
測定方向が140mm、測定方向と直交する方向が20mmの短冊状の試験片を作製した。万能引張試験機「DSS-100」(島津製作所製)を用いて、試験片の両端をチャックで片側20mmずつ把持(チャック間距離100mm)して、雰囲気温度23℃、引張速度200mm/minの条件にて引張試験を行い、引張破断時の強度(応力)を引張破断強度(MPa)、伸びを引張破断伸度(%)とした。
原料チップ0.1g、またはラベル0.1gを精秤し、25mlのフェノール/テトラクロロエタン=3/2(質量比)の混合溶媒に溶解した後、オストワルド粘度計で30±0.1℃で測定した。極限粘度[η]は、下式(Huggins式)によって求められる。
ここで、ηsp:比粘度、t0:オストワルド粘度計を用いた溶媒の落下時間、t:オストワルド粘度計を用いたチップ(またはラベル)溶液の落下時間、C:チップ(またはラベル)溶液の濃度である。なお、実際の測定では、Huggins式においてk=0.375とした下記近似式で極限粘度を算出した。
下記実施例および比較例で作製したフィルムロールを約242mm幅にスリットした上で、所定の長さに分割して巻き取ることによって小型のスリットロールを作製した。このスリットロールに、東洋インキ社製の草・金・白色のインキを用いて、ラベル用の印刷(3色印刷)を繰り返し施した。また、ラベル毎に、フィルムの長手方向にフィルム全長手方向に亘るミシン目(約1mm径の穴が約4mm間隔で並ぶミシン目)を約22mmの間隔で2本平行に形成した。熱収縮性フィルムの両端部をジオキソランで接着することにより、円筒状の熱収縮性ラベル(熱収縮性フィルムの主収縮方向を周方向としたラベル)を作製した。その後、長手方向に210mmピッチでカットして熱収縮性ラベルとし、500mlの角型PETボトル(胴部は1辺55mmの断面正方形、ネック部の最小部は1辺25mmの断面正方形)にラベルを被せ、ゾーン温度80℃のFuji Astec Inc製スチームトンネル(型式;SH-1500-L)内を、2.5秒で通過させることにより、ラベルを熱収縮させてボトルに装着した。なお、装着の際には、ネック部において1辺31mmの正方形部分がラベルの上端になるように調整した。
ラベルの装着完了後のPETボトルを24本毎に段ボール箱に詰め、夏場の倉庫での保管を想定し、45℃の環境試験室で60日間保管した。
エージング後のPETボトル胴部に接していたラベルについて、各物性を測定した。また、実施例5においては、ラベル外側のポリエステル層についての物性を測定した。なお、印刷部は、メチルエチルケトンを布にしみこませ、この布で拭き取って除去した。
収縮後の仕上がり性として、ラベルの歪み、すなわちタテヒケがないかを評価した。具体的には、ラベルの鉛直方向の長さを測定し、最大値と最小値の差が3mm以下であれば○、3mmを超えていれば×とした。
上記のエージング後のPETボトルが詰まった段ボール箱を3箱トラックの荷台に載せ、合計48時間以上となるよう、トラックを走行させた。段ボール箱からPETボトルを取り出し、目視でラベルのクラックの有無を調査した。72本のPETボトルのうち、1本でもクラックが入っていた場合は×、クラックが全くない場合は○として評価した。
[ポリエステル原料の調製]
合成例1(ポリエステルの合成)
エステル化反応缶に、57036質量部のテレフタル酸(TPA)、33244質量部のエチレングリコール(EG)、15733質量部のネオペンチルグリコール(NPG)、重縮合触媒として23.2質量部の三酸化アンチモン、5.0質量部の酢酸ナトリウム(アルカリ金属化合物)および46.1質量部のトリメチルホスフェート(リン化合物)を仕込み、0.25MPaに調圧し、220~240℃で120分間撹拌することによりエステル化反応を行った。反応缶を常圧に復圧し、3.0質量部の酢酸コバルト・4水塩、および124.1質量部の酢酸マグネシウム・4水塩を加え、240℃で10分間撹拌した後、75分かけて1.33hPaまで減圧すると共に、280℃まで昇温した。280℃で溶融粘度が4500ポイズになるまで撹拌を継続(約70分間)した後、ストランド状で水中に吐出した。吐出物をストランドカッターで切断することにより、チップBを得た。チップBの極限粘度は0.75dl/gであった。
合成例1と同様な方法により、表1に示した組成のチップA、Cを得た。表中、DEGはジエチレングリコール、PDは1,3-プロパンジオールの略記である。なお、チップAには、滑剤としてSiO2(富士シリシア社製サイリシア266)をポリエステルに対して2,000ppmの割合で添加した。極限粘度は、チップAが0.75dl/g、チップCが0.92dl/gであった。
<熱収縮性フィルムの製造方法>
上記したチップA、チップBおよびチップCを別個に予備乾燥し、表3に示したように、チップA20質量%、チップB70質量%およびチップC10質量%で混合して押出機に投入した。この混合樹脂を260℃で溶融させてTダイから押し出し、表面温度30℃に冷却された回転する金属ロールに接触させて急冷することにより、厚さ121μmの未延伸フィルムを得た。このときの未延伸フィルムの引き取り速度(金属ロールの回転速度)は約20m/minであった。また、未延伸フィルムのTgは73℃であった。
得られた縦延伸後のフィルムをテンター(横延伸機)へ導いた。予熱工程の温度を100℃、延伸工程の温度を75℃とし、幅方向に4.5倍に延伸した。横延伸後のフィルムを88℃で8秒間、緊張状態で熱処理した。その後、冷却し、両縁部を裁断除去して幅800mmでロール状に巻き取ることによって、厚さ18μmの延伸フィルムを所定の長さにわたって連続的に製造した。得られたフィルムと、得られたフィルムから作製し、熱収縮させてエージングした後のラベルの物性を上記した方法によって評価した。評価結果を表4に示した。表4Aにはフィルムの特性結果を、表4Bにはエージング後のラベル特性結果をそれぞれ示す(以下、同じ)。クラックの発生がなく、良好なラベルであった。
溶融温度を280℃に上げた以外は実施例1と同様にして、厚さ18μmのフィルムを製造した。評価結果を表4に示す。フィルムのときより、エージングによって極限粘度は若干低下したが、クラックの発生がなく、良好なラベルであった。
チップA、チップBおよびチップCを、質量比30:60:10に変更した以外は実施例1と同様にして、厚さ18μmのフィルムを製造した。評価結果を表4に示す。フィルムのときより、エージングによってTg前後の比熱容量差ΔCpは低下したが、クラックの発生がなく、良好なラベルであった。
未延伸フィルムの厚みを60μmにした以外は実施例1と同様にして、厚さ9μmのフィルムを製造した。評価結果を表4に示す。クラックの発生がなく、良好なラベルであった。
共押出法を利用して、コア層形成用樹脂、スキン層形成用樹脂、接着剤層形成用樹脂を別々の押出機(第一~第三押出機)から溶融押出しし、ダイス(Tダイ)内で積層し、エアーナイフ法により、30℃に冷却された回転する金属ロールに巻き付けて急冷することにより、厚さが121μmで、三種五層構成、すなわち、コア層の表裏両側に中間層(接着剤層)が積層され、それらの中間層の外側に、それぞれスキン層が積層された構成の未延伸フィルム(ポリスチレン系樹脂積層シート)を得た。未延伸フィルムの各層の形成方法(溶融押出までの工程)は、以下の通りである。なお、以下の説明においては、ポリスチレン系樹脂積層シートの表側から順に、第一層、第二層、第三層、第四層、第五層という(すなわち、第五層の表面は、金属ロール接触面である)。このときの未延伸フィルムの引取速度(金属ロールの回転速度)は、約20m/minであった。
上記したチップAとBを、それぞれブレンダー装置を用いて予備乾燥した後、その予備乾燥後のチップAを25質量部とチップBを65質量部とチップCを10質量部とをブレンダーにて混合させた後、第一押出機の直上のホッパに、定量スクリューフィーダーで連続的に供給した。そして、供給されたチップA~Cの混合物を、単軸式の第一押出機のTダイから260℃で溶融押出しした(コア層の表裏の外側に積層された中間層の外側に積層されるように溶融押出しした)。Tダイからの押出を安定させるために、押出機とTダイとの間にヘリカルタイプかつ並列タイプのギアポンプを介在させた。
上記したチップDを、ブレンダー装置を用いて予備乾燥した後、その予備乾燥後のチップDを、第二押出機の直上のホッパに、定量スクリューフィーダーで連続的に供給した。そして、供給されたチップDを、単軸式の第二押出機のTダイから溶融押出しした(コア層の表裏の外側に積層されるように溶融押出しした)。なお、第二押出機の温度は200℃に調整した。また、第一押出機による押出しと同様に、Tダイからの押出を安定させるために、押出機とTダイとの間にヘリカルタイプかつ並列タイプのギアポンプを介在させた。
上記したチップE,F,Gを、それぞれ、ブレンダー装置を用いて予備乾燥した後、それらのチップE,F,Gを、混合ミキサー内へ、定量スクリューフィーダーで連続的に別々に供給した。なお、チップEの供給量を43質量%とし、チップFの供給量を43質量%とし、チップGの供給量を14質量%とした。その後、混合ミキサー内で混合したチップE,F,Gの混合原料を、第三押出機の直上のホッパに、定量スクリューフィーダーで連続的に供給した。そして、供給されたチップE,F,G(混合済みのもの)を、単軸式の第三押出機のTダイから溶融押出しした。なお、第三押出機の温度も200℃に調整した。また、第一押出機による押出しや第二押出機による押出しと同様に、Tダイからの押出を安定させるために、押出機とTダイとの間にヘリカルタイプかつ並列タイプのギアポンプを介在させた。
上記各押出機による樹脂の押出において、未延伸フィルムの形成における第一~第三押出機の吐出量は、第一層/第二層/第三層/第四層/第五層の厚みが、33/3/49/3/33(総厚み121μm)となるように調整した。評価結果を表4に示す。クラックの発生もなく、良好なラベルであった。
溶融温度を310℃に上げた以外は実施例1と同様にして、厚さ18μmのフィルムを製造した。評価結果を表4に示した。フィルムのときより、エージングによって長手方向の引張破断伸度、極限粘度、Tg前後の比熱容量差ΔCpが低下し、クラックが発生し、不適なラベルであった。
チップAとチップBの質量比を30:70に変更した以外は実施例1と同様にして、厚さ18μmのフィルムを製造した。評価結果を表4に示す。フィルムの長手方向の収縮率が高く、タテヒケが発生し、不適なラベルであった。
チップA、チップBおよびチップCの質量比を5:80:15にした以外は実施例2と同様にして、厚さ18μmのフィルムを製造した。評価結果を表4に示す。エージングにより、極限粘度と引張破断伸度が低下し、クラックも発生して、不適なラベルであった。
未延伸フィルムの厚みを27μmにした以外は実施例2と同様にして、厚さ4μmのフィルムを製造した。エージングにより極限粘度が若干低下しただけであったが、ラベルの厚みが薄いため、クラックが発生し、不適なラベルであった。
未延伸フィルムの厚みを270μmにした以外は比較例1と同様にして、厚さ40μmのフィルムを製造した。評価結果を表4に示した。エージングにより極限粘度は低下したが、ラベルの厚みが厚いため、クラックの発生はなかった。
Claims (4)
- 以下の(1)~(6)の要件を満足することを特徴とするポリエステル系ラベル。
(1)ラベルの基材フィルムの厚みが8μm以上30μm以下
(2)ラベルを構成するポリエステルの極限粘度が0.58dl/g以上
(3)ラベルの主収縮方向および主収縮方向に対して直交する方向の引張破断伸度がいずれも5%以上
(4)ラベルを構成する基材フィルムについて偏光ATR法で1340cm-1の吸光度と1410cm-1の吸光度を求めた場合、ラベル主収縮方向の吸光度比(1340cm-1/1410cm-1)と、ラベルの主収縮方向に対して直交する方向の吸光度比(1340cm-1/1410cm-1)との差が0.2以上
(5)ラベルを構成する基材フィルムについて温度変調示差走査熱量計で可逆熱容量曲線を測定したときのTg前後の比熱容量差ΔCpが、0.2J/(g・℃)以上
(6)ラベルの鉛直方向の長さの最大値と最小値の差が3mm以下 - ラベルの主収縮方向に対して直交する方向の引張破断強度が5MPa以上60MPa以下である請求項1に記載のポリエステル系ラベル。
- ラベルを構成するポリエステルが、ポリエステルを構成するユニット100モル%中、プロパンジオール由来のユニットを5モル%以上15モル%以下有する請求項1または2に記載のポリエステル系ラベル。
- 請求項1~3のいずれかに記載のラベルを容器の外周の少なくとも一部に有することを特徴とする包装容器。
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