Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets

Definitions

• the present invention relates to a biaxially oriented polyester film and a method for producing a biaxially oriented polyester film.
• the present invention relates to a biaxially oriented polyester film used in the field of packaging such as foods, pharmaceuticals, and industrial products, and a method for producing the biaxially oriented polyester film.
• the present invention relates to a biaxially oriented polyester film containing a polyethylene terephthalate resin as a main component, which has excellent puncture resistance and excellent laminate strength on both sides (face and face) of the film.
• Polyethylene terephthalate (hereinafter, referred to as “polyethylene terephthalate” is abbreviated as “Mita”)
• Polyethylene terephthalate (hereinafter, abbreviated as “polyethylene terephthalate” is abbreviated as “Mita”) resin.
• Applications are also being considered in the fields of films, vacuum insulation materials, drawing films, and film for can inner bags.
• Patent Document 1 For example, in Patent Document 1, 40 to 80% by weight of Mingo resin is used with respect to Mingo resin, and tensile elastic moduli in the longitudinal direction and the width direction are set to 2.3 to 3.503. It is disclosed that it can be suitably used as a polyester film for an inner bag of a can.
• Patent Document 2 four directions (0° (longitudinal direction), 45°, 90° (width direction)
• Used packaging material from the outside consisting of construction of the base layer _ gas barrier layer _ sealant layer is disclosed. Then, by setting the number of pinholes when the packaging material is bent 100 times under the condition of 5 1 X 40% [3 ⁇ 4 1 to 1 to 3 or less, liquid filling excellent in aroma retention is achieved. It is disclosed that it can be preferably used as a packaging material.
• Patent Document 3 a Mihinoto resin 6 0 wt% or more, the longitudinal direction and the width direction of the yield stress 7 0 IV!? 3 or more, the breaking strength of 1 6 0 IV!? 3 or more, break It is disclosed that when the elongation is 100% or more, it can be suitably used for nylon film and other flexible film applications.
• Patent Document 1 Patent No. 6 1 9 5 7 6 5
• Patent Document 2 Patent No. 6 3 4 7 4 9 9 Publication
• Patent Document 3 Patent No. 5 9 9 4 8 6 4 gazette Summary of invention
• the film surface (the surface opposite to the surface where the film is in contact with the cooling port) is in the slow cooling state, so the film surface (the surface where the film is in contact with the cooling port) It is assumed that the crystallinity is higher than that of In Patent Document 2, the cooling water is relatively high at 20 ° and it is presumed that crystallization will proceed.
• the film surface with a high degree of crystallinity may have a low laminating strength, and when the bag-making product is dropped, it tends to peel off between the laminated layers and break the bag.
• an object of the present invention is to provide a biaxially oriented polyester film having both good bag breaking resistance and good laminate strength on both sides of the film. Moreover, it is providing the manufacturing method of the said biaxially oriented polyester film. ⁇ 02020/175066 3 ⁇ (: 171?2020/004369
• the present inventors have earnestly studied a biaxially oriented polyester film. As a result, it was found that good lamination strength and good bag-breaking resistance can be obtained on both sides of the film by setting the Mending resin ratio within a specific range and reducing the difference in crystallinity on both sides of the film. Came to complete the present invention
• the difference (absolute value) between the ratio of one surface/Mitsumi and the ratio of the other surface/Mimi is 0. 1 or less.
• the difference is 0.1 or less and the crystallinity on one side is the same as the crystallinity on the other side, the difference in laminating strength between one side and the other side is small. It gets worse. As a result, it is possible to suppress the concentration of stress on the surface having a low laminate strength, and it is possible to improve the laminate strength regardless of which surface is used. As a result, the bag breaking resistance can be improved.
• the polyester resin composition contains a polyester resin (Mitsumi) other than the polyethylene terephthalate resin (8).
• the polyester resin composition contains a polyester resin (Mitsumi) other than the polypropylene terephthalate resin (8), the film-forming property during biaxial stretching and the mechanical properties of the obtained film can be adjusted.
• the three-dimensional average roughness on the one surface of the biaxially oriented polyester film is 3 3 and the three-dimensional average roughness on the other surface 3 It is preferable that the difference (absolute value) from 3 is 0.01 or less.
• the difference is 0.010 or less, it is possible to prevent the difference between the laminating strength of the one surface and the laminating strength of the other surface from becoming too large. That is, it is possible to suppress the concentration of stress on the surface having a low laminate strength, and to further improve the bag puncture resistance.
• the refractive index N 2 in the thickness direction of both surfaces of the biaxially oriented polyester film is from 1.480 to 1.510.
• the biaxially oriented polyester film has a laminating strength of 4. The above is preferable.
• the laminating strengths of the one surface and the other surface of the biaxially oriented polyester film are both 4. If the above is satisfied, it is possible to suppress the bag from being broken from the laminated part when the bag is prepared and dropped parallel to the floor, and the bag has excellent bag-breaking resistance.
• the present invention also relates to the method for producing a biaxially oriented polyester film, which comprises a step of casting a resin composition for producing a biaxially oriented polyester film in a cooling port to form an unstretched sheet.
• the unstretched sheet on the cooling port is blown with a wind of 5° or less. ⁇ 02020/175066 5 ⁇ (: 171?2020/004369
• Fig. 1 is a schematic front view for explaining a method of blowing cooling air from a multi-duct onto a mound surface of an unstretched sheet on a cooling port.
• Fig. 2 is a side view of Fig. 1.
• Parts by weight and “parts by weight” are treated as synonyms.
• the biaxially oriented polyester film according to the present embodiment is
• the polyester resin composition is mainly composed of Mingo resin (), and the content of Mingo resin (8) in the polyester resin composition is preferably 60% by weight or more, Wt% or more is preferable, and further 8 ⁇ 02020/175066 6 ⁇ (: 171?2020/004369
• the puncture strength can be made sufficient and the bag puncture resistance can be improved.
• the Mingo resin (8) which is used as a main component, preferably contains terephthalic acid in an amount of 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol%. % And more preferably 100 mol%.
• 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more.
• the lower limit of the intrinsic viscosity of the above-mentioned Mingko resin (8) is preferably 0.8 ⁇ / 9 , more preferably ⁇ 9.5 ⁇ / 9 , and further preferably 1.0 ⁇ / 9 Is.
• the upper limit of the intrinsic viscosity of the Mouto resin () is preferably 1.3 ⁇ / 9 . 1 With ⁇ / 9 or less, to suppress a high stress during film stretching Risugiru, the film-forming property can be improved. Furthermore, when using Mending resin with a high intrinsic viscosity, the melting temperature of the resin increases, so it is necessary to raise the extrusion temperature.However, the Mending resin with an intrinsic viscosity of 1.3 I/9 or less ( By using (8), it is not necessary to perform high temperature extrusion, and the generation of decomposition products can be suppressed.
• the polyester resin composition contains a polyester resin (M) other than the Ming resin (8) for the purpose of adjusting film-forming properties during biaxial stretching and the mechanical properties of the obtained film. Is preferred.
• polyester resin examples include polyester, polyethylene naphthalate, polypropylene naphthalate, polypropylene terephthalate and the like, or isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, cyclohexanedicarboxylic acid. Acid, adipic acid, azelaic acid and sebacic acid. ⁇ 02020/175066 7 ⁇ (: 171?2020/004369
• the resin mainly composed of mitoba has a high melting point, is excellent in heat resistance, has good compatibility with mitoba resin and is excellent in transparency, and therefore mitoba resin or copolymerized mitoba resin is preferable. Mingko resin is particularly preferable.
• the addition amount of the polyester resin (Mitsumi) is preferably 40% by weight or less, more preferably 35% by weight or less, and further preferably 15% by weight based on the whole polyester resin composition. It is less than or equal to weight %.
• the addition amount of the polyester resin (Mitsumi) may be 0% by weight or more, 5% by weight or more, 10% by weight or more based on the whole polyester resin composition.
• the lower limit of the intrinsic viscosity of the polyester resin (Mitsumi) is preferably 0.5 I/
• the upper limit of the intrinsic viscosity of the polyester resin (Mitsumi) is preferably 1.3 ⁇ / 9 .
• the biaxially oriented polyester film contains, in addition to the polyester resin composition, conventionally known additives such as a lubricant, a stabilizer, a colorant, an antioxidant, an antistatic agent, and an ultraviolet absorber. It may be contained.
• the content of the polyester resin composition is preferably 99.5% by weight or more, and more preferably 99.6% by weight or more. , 99.7% by weight or more is more preferable.
• the content of the polyester resin composition is preferably 100% by weight or less, when the total amount of the biaxially oriented polyester film is 100% by weight, and 99.
• the lubricant is one that can adjust the dynamic friction coefficient of the film, and examples thereof include inorganic lubricants such as silica, calcium carbonate, and alumina, and organic lubricants. Silica and calcium carbonate are more preferable, and silica is particularly preferable because it reduces haze. By these, transparency and slipperiness can be exhibited.
• the lower limit of the content of the lubricant in the biaxially oriented polyester film is preferably 100 weight 01, and more preferably 800 weight 111. Sliding property can be improved by making it 100 weight or more.
• the upper limit of the content of the lubricant is preferably 2000% by weight 111, more preferably 100% by weight, and particularly preferably 180% by weight 111. The transparency can be maintained by adjusting the amount to be 200 weight or less.
• the biaxially oriented polyester film is composed of a laminate of less than 8 layers, each layer containing a polyester resin composition containing 60 to 100% by weight of a poly(ethylene terephthalate) resin (8). Preferably, it is composed of 3 layers or less ⁇ 02020/175066 9 ⁇ (: 171?2020/004369
• the biaxially oriented polyester film is laminated with less than 8 layers, the composition of each layer may be the same or different. It is also preferable that the biaxially oriented polyester film is composed of a single layer.
• the biaxially oriented polyester film according to the present embodiment can satisfy the following requirement (1) without being multilayered into eight layers or more.
• the biaxially oriented polyester film satisfies the following requirement (1).
• the difference (absolute value) between the ratio of one surface/Mitsumi and the ratio of the other surface/Mimi is 0. 1 or less.
• the difference is preferably 0.08 or less, more preferably 0.06 or less.
• Additional 1 4 5 0 ⁇ 1 0_Rei - 1 of the absorption intensity eighth peak is the absorption derived from the methylene group of the "type crystals Mihinoto, 1 4 1 0 ⁇ 1 0_Rei - absorption strength of 1 peak
• the degree is absorption derived from the carbon bond of the benzene ring.
• the value of the absorption intensity ratio of 8/M shows the orientation coefficient. The smaller the orientation coefficient, the lower the crystallinity, and the higher the orientation coefficient, the higher the crystallinity.
• the biaxially oriented polyester film has the difference of 0.1 or less and the same crystallinity, and therefore the difference in the laminating strength between the one surface and the other surface is small. As a result, it is possible to suppress the concentration of stress on the surface having a low laminate strength, and it is possible to obtain sufficient bag breakage resistance.
• the difference and the absorption intensity ratio of 8/M are in the direction of setting the measurement sample.
• the measured value is used as the direction. This is, This is because the measured value of direction more clearly reflects the crystallinity.
• a more detailed measuring method is according to the method described in the examples.
• the biaxially oriented polyester film to be measured is a single-wafer film, ⁇ 02020/175066 10 ((171?2020/004369
• the direction may be unknown.
• the absorption intensity ratios of 8/M in the plural directions are obtained, and the direction in which the difference is the largest is the IV!0 direction.
• the lower limit of the ratio of the absorption intensity to the absorption intensity and the value of the / is preferably 0.2 in any one of the one surface and the other surface. .. It is more preferably 0.3 and even more preferably 0.4.
• the ratio 8/M is 0.2 or more, the orientation becomes higher, the crystallinity becomes higher, and the mechanical strength can be made more sufficient.
• the upper limit of the value of the ratio Hachi/Mimi is preferably 0.9. More preferably, it is 0.8, and even more preferably 0.7.
• the ratio 8/M is 0.9 or less, the orientation does not become too high and the crystallinity can be made moderate. As a result, the affinity with the adhesive can be increased, and the laminating strength can be made more sufficient. In addition, the bag-breaking resistance can be sufficient.
• the three-dimensional average roughness 33 on the one surface of the biaxially oriented polyester film and the three-dimensional average roughness 3 on the other surface The upper limit of the difference (absolute value) from 3 is 0.010. It is preferably 0.08 0 1, more preferably 0 0 0 6 0!. When the difference is 0.01 0 111 or less, the difference between the laminating strength on the one surface and the laminating strength on the other surface is prevented from becoming too large. That is, it is possible to prevent the stress from concentrating on the surface having a low laminate strength, and to provide sufficient bag breakage resistance.
• the lower limit of 3 is preferably 0. 01. More preferably, it is 0.02, and even more preferably 0.03 111.
• Three-dimensional average roughness of the one surface of the biaxially oriented polyester film 3 3 and three-dimensional average roughness of the other surface 3 The upper limit of 3 is preferably 0.10. It is more preferably 0.08, and further preferably 0.06. The three-dimensional average roughness If it is 10 or less, the fill ⁇ 02020/175066 11 ⁇ (: 171? 2020 /004369
• the lower limit of the value of the refractive index in the thickness direction of the one surface and the value of the refractive index in the thickness direction of the other surface of the biaxially oriented polyester film is preferably 1.480. It is more preferably 1.485 and even more preferably 1.
• the upper limit of the value of the refractive index in the thickness direction of the one surface and the value of the refractive index in the thickness direction of the other surface of the biaxially oriented polyester film is preferably 1.510. More preferably 1.505, and even more preferably 1.
• the puncture strength can be further increased, and as a result, the bag puncture resistance can be made more sufficient.
• the laminating strengths of the one surface and the other surface of the biaxially oriented polyester film are both 4.0.
• the above is preferable. More preferably 5. And more preferably 6.01 ⁇ 1/15. Four. If the above is satisfied, it is possible to suppress the bag from being broken from the laminated part when the bag is prepared and dropped flat on the floor, and the bag is more resistant to bag breaking.
• the lower limit of the heat shrinkage rate of the biaxially oriented polyester film after heating for 15 minutes at 150° in the IV! 0 direction for 15 minutes is preferably 0.5%. It is more preferably 0.8% and even more preferably 1.2%. ⁇ When it is 5% or more, the puncture strength can be increased and the bag puncture resistance can be maintained high.
• the upper limit of the heat shrinkage rate of the biaxially oriented polyester film after heating at 150° for 15 minutes in the IV!0 direction for 15 minutes is preferably 3.5%. It is more preferably 3.0% and even more preferably 2.5%. When it is 3.5% or less, it is possible to prevent the film from being greatly shrunk when heat is applied in the post-processing, and the processing becomes easier.
• the lower limit of the puncture strength of the biaxially oriented polyester film is 0.4! ⁇ 1/ ⁇ 0 2020/175 066 12 ⁇ (: 17 2020 /004369
• the upper limit of the puncture strength of the biaxially oriented polyester film is preferably 0.91 ⁇ 1/. It is more preferably ⁇ 8 1 ⁇ 1/, and even more preferably ⁇ .
• the lower limit of the degree of plane orientation ( ⁇ ) of the biaxially oriented polyester film is 0.14.
• 5 is preferable. It is more preferably 0.148, and even more preferably 0.151. ⁇ When it is not less than 0.145, the plane orientation is sufficiently strong, the puncture strength is improved, and the bag breaking resistance is more sufficient.
• the upper limit of ⁇ of the biaxially oriented polyester film is preferably 0.200
• the improvement effect can be sufficiently obtained.
• the lower limit of the thickness of the biaxially oriented polyester film is preferably 5. It is more preferably 7, and even more preferably 90! When it is at least 50!, the strength as a film can be made sufficient.
• the upper limit of the thickness of the biaxially oriented polyester film is preferably 40. It is more preferably 30 and even more preferably 20.
• the biaxially oriented polyester film preferably has the same composition over the entire area of the film.
• a printing layer may be laminated on the biaxially oriented polyester film.
• water-based and solvent-based resin-containing printing inks can be preferably used as the printing ink for forming the printing layer.
• the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof.
• Printing inks include known antistatic agents, light blocking agents, UV absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, defoamers, cross-linking agents, anti-blocking agents, antioxidants, etc. The additive may be included. ⁇ 02020/175066 13 ((171?2020/004369
• the printing method for providing the printing layer is not particularly limited, and known printing methods such as an offset printing method, a gravure printing method, and a screen printing method can be used.
• known drying methods such as hot air drying, hot air drying, and infrared drying can be used.
• the biaxially oriented polyester film may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, surface roughening treatment, as long as the object of the present invention is not impaired.
• Known anchor coat treatment, printing, decoration and the like may be applied.
• a gas barrier layer such as an inorganic thin film layer or a metal foil such as an aluminum foil can be provided on at least one surface of the biaxially oriented polyester film.
• the inorganic thin film layer is a thin film made of metal or inorganic oxide.
• the material for forming the inorganic thin film layer is not particularly limited as long as it can form a thin film, but from the viewpoint of gas barrier properties, inorganic oxides such as silicon oxide (silica), aluminum oxide (alumina), and a mixture of silicon oxide and aluminum oxide. The thing is preferably mentioned. In particular, a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of achieving both flexibility and denseness of the thin film layer.
• the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% by weight in terms of metal content. If the Hachijo concentration is 20% or more, the water vapor gas barrier property can be further enhanced. On the other hand, when the content is 70% or less, the inorganic thin film layer can be softened, and it is possible to prevent the film from being destroyed during the secondary processing such as printing or laminating, thereby lowering the gas barrier property.
• the term "silicon oxide” as used herein refers to various silicon oxides such as 3 O and 3 I 0 2 or a mixture thereof
• aluminum oxide refers to various aluminum oxides such as 8 O and 8 O 2 O 3 . Or a mixture thereof.
• the thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 n. If the thickness of the inorganic thin film layer is 1 nm or more, more satisfactory gas barrier properties ⁇ 02020/175066 14 ⁇ (: 171?2020/004369
• the method of forming the inorganic thin film layer is not particularly limited, and examples thereof include physical vapor deposition methods such as vacuum vapor deposition method, sputtering method, and ion plating method ( ⁇ method).
• a known vapor deposition method such as a chemical vapor deposition method ( ⁇ 30 method) may be appropriately adopted.
• a typical method for forming the inorganic thin film layer will be described by taking a silicon oxide/aluminum oxide thin film as an example.
• a mixture of 3 ⁇ 2 and eight ⁇ 2 ⁇ 3 as evaporation raw material, or 3 ⁇ 2 and eight ⁇ mixtures are preferably used.
• Particles are usually used as these vapor deposition raw materials. At that time, it is desirable that the size of each particle is such that the pressure during vapor deposition does not change. Is.
• resistance heating, high frequency induction heating, electron beam heating, laser heating, and other methods can be adopted.
• the reaction gas it is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor or the like as the reaction gas, or employ reactive vapor deposition using means such as ozone addition or ion assist.
• the deposition conditions can be arbitrarily changed, such as applying a bias to the material to be vapor-deposited (a laminated film to be subjected to vapor deposition) or heating or cooling the material to be vapor-deposited.
• the vapor deposition material, reaction gas, bias of the object to be vapor-deposited, heating/cooling, etc. can be similarly changed when the sputtering method or the zero method is adopted.
• a printing layer may be laminated on the inorganic thin film layer.
• the gas barrier layer made of metal oxide is not a completely dense film, but has small defects.
• the resin in the resin composition for the protective layer penetrates into the defective portion of the metal oxide layer.
• the gas barrier property is stabilized.
• the gas barrier performance of the laminated film will be greatly improved.
• a curing agent such as an epoxy-based, isocyanate-based, or melamine-based is added.
• solvent (solvent) used when forming the protective layer examples include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate; Ester solvents such as butyl acetate; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, etc. may be mentioned.
• the polar group of the urethane bond interacts with the inorganic thin film layer and also has flexibility due to the presence of the amorphous portion, so that the inorganic thin film layer is also subjected to bending load. It is preferable because damage to the can be suppressed.
• the acid value of urethane resin is 10 to 6 And more preferably within the range of When the acid value of the fat is within the above range, the liquid stability is improved when it is made into an aqueous dispersion, and the protective layer can be uniformly deposited on the highly polar inorganic thin film, resulting in a good coat appearance. Becomes
• the urethane resin preferably has a glass transition temperature (Ding 9) is 8 0 ° ⁇ As, more preferably 9 0 ° ⁇ As.
• Ding 9 glass transition temperature
• urethane resin it is more preferable to use a urethane resin containing an aromatic or araliphatic diisocyanate component as a main constituent from the viewpoint of improving gas barrier properties.
• the metaxylylene diisocyanate component it is particularly preferable to contain the metaxylylene diisocyanate component.
• the aromatic or araliphatic diisocyanate in the urethane resin is ⁇ 02020/175066 16 ⁇ (: 171?2020/004369
• the proportion of anate is preferably in the range of 50 mol% or more (500 to 100 mol%) in 100 mol% of the polyisocyanate component ().
• the proportion of the total amount of the aromatic or araliphatic diisocyanate is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, further preferably 80 to 100 mol%. is there.
• "Yukerack (registered trademark) ⁇ ZV P B" series commercially available from Mitsui Chemicals, Inc. can be preferably used.
• the proportion of the total amount of aromatic or araliphatic diisocyanate is 50 mol% or more, better gas barrier properties can be obtained.
• the urethane resin preferably has a carboxylic acid group (carboxyl group).
• carboxylic acid (salt) group for example, a polyol component having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid may be introduced as a copolymerization component. ..
• a urethane resin of an aqueous dispersion can be obtained by synthesizing a carboxylic acid group-containing urethane resin and then neutralizing it with a salt forming agent.
• the salt forming agent include ammonia, trimethylamine, triethylamine, triisopropylamine, tree 11-propylamine, tree 1!-trialkylamines such as butylamine, 1 ⁇ 1-methylmorpholine, 1 ⁇ 1.
• Examples include 1 ⁇ 1-alkylmorpholines such as ethylmorpholine, 1 ⁇ 1-dimethylethanolamine, and 1 ⁇ 1-dialkylalkanolamines such as 1 ⁇ 1_diethylethanolamine. These may be used alone or in combination of two or more.
• a layer of another material may be laminated on the biaxially oriented polyester film, and as a method thereof, the biaxially oriented polyester film may be attached after being produced or may be attached during film formation.
• the biaxially oriented polyester film is used, for example, as a packaging material by providing an inorganic vapor deposition layer on the biaxially oriented polyester film and further forming a heat-sealable resin layer (also referred to as a sealant layer) called a sealant. be able to.
• the heat-sealable resin layer is usually formed by an extrusion laminating method or ⁇ 02020/175066 17 ((171?2020/004369
• thermoplastic polymer forming the heat-sealable resin layer may be any one as long as it can sufficiently exhibit sealant adhesiveness, Polyethylene resin such as Mami and polypropylene resin. Ethylene-vinyl acetate copolymer, ethylene-olefin-random copolymer, ionomer resin and the like can be used.
• the sealant layer may be a monolayer film or a multilayer film, and may be selected according to the required function.
• a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used.
• the sealant layer may be mixed with various additives such as a flame retardant, a slip agent, an anti-blocking agent, an antioxidant, a light stabilizer and a tackifier.
• the thickness of the sealant layer is preferably from 10 to 1001 and more preferably from 20 to 600!.
• the biaxially oriented polyester film can be used as a base film (base layer) of a packaging laminate.
• base layer is used to represent the layer boundary.
• base layer/gas barrier layer/protective layer base layer/gas barrier layer/protective layer/adhesive layer/sealant layer
• base layer Material layer/gas barrier layer/protective layer/adhesive layer/resin layer/adhesive layer/sealant layer base material layer/adhesive layer/resin layer/gas barrier layer/protective layer/adhesive layer/sealant layer
• base Material layer/gas barrier layer/protective layer/printing layer/adhesive layer/sealant layer base material layer/printing layer/gas barrier layer/protective layer/adhesive layer/sealant layer
• a laminate using the biaxially oriented polyester film is used for packaging products, ⁇ 0 2020/175 066 18 ⁇ (: 171? 2020 /004369
• the thickness of the laminate can be appropriately determined according to its application. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500, preferably about 10 to 300.
• the die method is preferable from the viewpoint of thickness accuracy in the width direction.
• the draw ratio is difficult to increase due to the manufacturing method, and thickness defects in the width direction may occur.
• a resin having the same composition is multilayered into eight layers or more by a static mixer or the like. Therefore, a method for obtaining a uniform unstretched sheet by suppressing crystallization has been proposed.However, from the viewpoint of facility simplicity and maintainability, the following casting method for obtaining a homogeneous unstretched sheet is used.
• melt-extruding it is preferable to form a laminate of less than 8 layers. The number of laminated layers is more preferably 3 or less. In terms of equipment maintenance, single layer is the most preferable.
• a layer structure of 2 types 2 layers, 2 types 3 layers, or 3 types 3 layers is preferable.
• the lower limit of the intrinsic viscosity of the unstretched sheet obtained is preferably 0.7. More preferably ⁇ . 7 5 was ⁇ / 9, more preferably from ⁇ . 8 0 ⁇ / 9, particularly preferably 0. 9 0_Rei_1 ⁇ / 9. When it is 0.70 ⁇ 1 /9 or more, crystallization during casting is suppressed, and the yield stress of the unstretched sheet becomes low, and as a result, breakage tends not to occur during stretching.
• the upper limit of the intrinsic viscosity of the obtained unstretched sheet is preferably 1.2 ⁇ / 9 , more preferably 1.1 ⁇ / 9 . ...! .2 ⁇ / 9 or less ⁇ 02020/175066 19 ⁇ (: 171?2020/004369
• the stress during stretching does not become too high, and the film-forming property becomes better.
• the lower limit of the die temperature is preferably 2400°, more preferably 2450°, and particularly preferably 250°. When it is at least 240°, the discharge becomes more stable and the thickness can be made more uniform.
• the temperature is 240° or more, it is possible to prevent the resin remaining in the resin melt extrusion step from becoming an unmelted substance and being mixed into the film, thereby impairing the film quality. it can.
• the upper limit of the resin melting temperature is preferably 275 ° , more preferably 270°, and most preferably 265°. When it is at most 27.5 ° , the decomposition of the resin can be suppressed and the film can be prevented from becoming brittle. Further, the inherent viscosity of the obtained film can be maintained high, and the film-forming property can be further improved.
• the upper limit of the die temperature is preferably from 3 0 0 ° ⁇ , more preferably 2 9 0 ° ⁇ or less, more preferably 2 8 0 ° ⁇ below.
• it is 300° or less, it is possible to prevent the thickness from becoming uneven. Further, it is possible to prevent the appearance of the resin from being deteriorated due to stains on the die lip or the like.
• the lower limit of the rotation number of the screw in the resin melt extrusion step is preferably 7
• the ejection is more stable and the thickness is more uniform. Mixing is more sufficient and appearance defects can be further suppressed.
• the upper limit of the number of revolutions of the screw in the resin melt extrusion step is preferably 150 ", more preferably 1300", and particularly preferably 1100". Further, it is possible to prevent the decomposition of the molten resin from progressing due to shearing heat generation, to suppress the decrease in the intrinsic viscosity of the obtained film, and to improve the film-forming property.
• the upper limit of the cooling port temperature is preferably 40°, and more preferably 10° or less. If it is 40 ° C. or less, the crystallinity of the molten polyester resin composition upon cooling and solidification does not become too high, and the stretching becomes easier. In addition, ⁇ 0 2020/175 066 20 ⁇ (: 17 2020 /004369
• the mint strength can be increased and the bag puncture resistance can be improved.
• the lower limit of the cooling port temperature is preferably 0°. When it is ⁇ °° or more, the effect of suppressing crystallization when the molten polyester resin composition is cooled and solidified can be sufficiently exerted. When the temperature of the cooling port is within the above range, it is preferable to reduce the humidity of the environment near the cooling port to prevent dew condensation.
• the temperature of the surface of the cooling hole rises because the high temperature resin comes into contact with the surface.
• the chill roll is cooled by injecting cooling water through the pipe inside, but to ensure a sufficient amount of cooling water, devise the arrangement of the pipe, and maintain the pipe so that sludge does not adhere to it. It is necessary to reduce the temperature difference across the width of the chill roll surface. In particular, unless the method of obtaining a uniform unstretched sheet by forming multiple layers of 8 layers or more is used, crystallization of the unstretched sheet is likely to proceed, so caution is required.
• the thickness of the unstretched sheet is preferably in the range of 15 to 2500. It is more preferably 500 or less, and further preferably 300 or less.
• step 8 From the viewpoint of reducing the difference in crystallinity between the surface of the unstretched sheet (the surface in contact with the cooling hole) and the surface of the wall (the surface on the side opposite to the surface in contact with the cooling hole), biaxial After the resin composition for producing an oriented polyester film is cast on the cooling port (after step 8), it is preferable to rapidly cool the face of the unstretched sheet on the cooling port. By rapidly cooling the face, the difference in crystallinity from the face is reduced, the laminar strength is improved, and the bag breaking resistance is improved as a result.
• the method of quenching is not particularly limited, but a method of blowing cooling air using a multi-duct is preferable from the viewpoint of facility simplicity and maintainability.
• the upper limit of the temperature of the cooling air is preferably 20 ° ⁇ , more preferably 5 ° ⁇ or less. When it is 20° or less, the crystallinity of the unstretched sheet's mound surface does not become high, the laminate strength can be maintained high, and the bag-breaking resistance can be further improved. ⁇ 0 2020/175066 21 ⁇ (: 171? 2020 /004369
• the lower limit of the temperature of the cooling air is 15 °. When it is at least _ 5 ° ⁇ , the effect of suppressing the crystallization of the sapphire surface of the unstretched sheet is sufficiently obtained.
• Fig. 1 is a schematic front view for explaining a method of blowing cooling air from a multi-duct onto the wall surface of an unstretched sheet on a cooling port
• Fig. 2 is a side view thereof.
• the die 10 is arranged so that the discharge port 12 faces the surface of the cooling port 20.
• the distance (shortest distance) between the discharge port 12 and the surface of the cooling port 20 is not particularly limited, but is generally about 20 to 100.
• a multi-duct 30 is arranged on the outer peripheral surface of the cooling port 20.
• the position of the multi-duct 30 is the rotation of the cooling hole 20 when the position of the die 10 is 0° with respect to the center of the cooling hole 20. It is preferably installed in the range of ⁇ to 45°, more preferably in the range of 10 to 35°, with respect to the direction (clockwise direction in Fig. 2).
• the multi-duct 30 is arranged within the above range, it is possible to cool the mound surface of the unstretched sheet 40 cast on the cooling hole 20 immediately after casting.
• the time from the time when the resin composition for producing the biaxially oriented polyester film is cast into the cooling port (the time when it is touched) to the time when the air is blown to the relevant part is within 2.0 seconds.
• the time is preferably within 1.0 second, more preferably within 0.5 second.
• the width of the multi-duct 30 (horizontal length in Fig. 1) is ⁇ 0 2020/175066 22 ⁇ (: 171? 2020 /004369
• the width of the unstretched sheet 40 is not less than that of the unstretched sheet 40.
• the vertical width of the multi-duct 30 (the length in the vertical direction in Fig. 1) is preferably not less than 3001 and not more than 80000! The following is more preferable.
• the speed at which the unstretched sheet 40 moves on the cooling port 20 is preferably 20
• a suitable amount of cooling air can be blown to the bottom surface of the unstretched sheet 40. it can.
• the upper limit of the height of the multi-duct 30 from the cooling port 20 is 200 or less, and more preferably 100 or less. When it is 200 or less, the cooling efficiency is improved, the effect of suppressing the crystallization of the face of the unstretched sheet 40 is sufficiently obtained, and the laminar strength can be increased.
• the lower limit of the height of the multi-duct 30 from the cooling port 20 is not particularly limited, but is preferably within a range where it does not come into contact with the unstretched sheet 40.
• the upper limit of the wind speed of the cooling air from the multi-duct 30 is preferably 2 It is 1 n, and more preferably 1800 1 /
• the lower limit of the cooling air velocity is preferably 5 0 111 /111 ⁇ . When it is at least 5 01/
• the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching, and is not particularly limited.
• the lower limit of the stretching temperature in the longitudinal direction (hereinafter, also referred to as IV! 0 direction) is preferably 55°, and more preferably 60°. If it is at least 55°, fracture can be further suppressed. Further, it is possible to prevent the orientation in the vertical direction from becoming too strong, and to suppress an increase in the thermal shrinkage in the IV! IV! 0 direction of the upper limit of the extension Shin temperature is preferably 1 hundred ° ⁇ , more preferably 9 5 ° ⁇ .
• the orientation can be sufficiently provided and the mechanical properties can be further enhanced.
• the lower limit of the draw ratio in the IV! 0 direction is preferably 2.5 times, and particularly preferably.
• the orientation can be sufficiently provided and the mechanical properties can be further enhanced. Further, when it is 2.5 times or more, the thickness unevenness can be suppressed and the slack of the film roll can be prevented.
• the upper limit of the draw ratio in the IV! 0 direction is preferably 3.8 times, and more preferably
• the lower limit of the stretching temperature in the width direction (hereinafter, also referred to as the "zero direction”) is preferably 55°, and more preferably 60 ° . If it is more than 55 ° , fracture will occur. ⁇ 02020/175066 24 ⁇ (: 171? 2020 /004369
• the upper limit of the stretching temperature Ding 0 direction is preferably 1 00 ° ⁇ , more preferably 95 ° ⁇ . When it is 100 ° or less, the orientation can be sufficiently provided, and the mechanical properties can be further enhanced.
• the lower limit of the draw ratio in the 0-direction is preferably 3.7 times, and more preferably
• the upper limit of the draw ratio in the 0-direction is preferably 5.0 times, and more preferably
• the lower limit of the heat setting temperature is preferably 185 ° ⁇ , more preferably 190 ° ⁇ . When it is 1 85° or more, the heat shrinkage rate can be further reduced.
• the upper limit of the heat setting temperature is preferably 220° ⁇ . If it is 220° or less, it is possible to prevent the film from melting and becoming extremely brittle.
• the heat setting temperature may be different between the face and the face. By varying the heat setting temperature between the face and the face, the crystallinity can be adjusted and the laminate strength can be further increased. As a result, the bag breaking resistance can be further enhanced.
• the temperature difference is preferably 10° ⁇ or more and 30°° or less, and more preferably 10°° or more and 20°° or less.
• the lower limit of the relaxation rate is preferably 0.5%. ⁇ When it is more than 0.5%, the heat shrinkage in the direction of the neck can be kept low.
• the upper limit of the relaxation rate is preferably 10%. When it is 10% or less, slack and the like can be prevented from occurring, and the flatness can be improved.
• the lower limit of the temperature for the relaxation process is preferably 130°°, and more preferably 150°°. If the film is at a temperature of 30° ⁇ ⁇ 02020/175066 25 ((171?2020/004369
• the upper limit of the relaxation temperature is preferably 190 ° ⁇ , more preferably 170° ⁇ . When it is 1 90° or less, it is possible to prevent the flatness of the film from being deteriorated due to wrinkles and the like.
• the puncture strength of the polyester film was calculated by converting the value measured by the test method described in "1 3-71 707" into 1 by the following formula.
• the medium crystal was brought into close contact with the film surface layer as diamond, and the spectral intensity was measured by the total reflection method while light was incident parallel to the IV!0 direction.
• the resolution of the spectrometer 4_Rei - 1 spectrum accumulation number was measured as 64 times.
• the spectral intensity is the absorbance at each wave number. It was calculated by the following formula.
• Absorbance ratio (8/M) Absorbance 8 Peak The scan Bae-vector strength) / absorbance only (1 4 1 0 scan Bae spectrum intensity of the peak of ⁇ 1 0_Rei 01 1), while the incident light parallel to the Ding 0 direction, by IV! 0 direction The spectrum strength was also measured by the same method as the measurement of 1.
• the average roughness of the film surface was measured by the stylus method under the following conditions using a contact-type three-dimensional surface roughness meter (Model: Mending_40008) manufactured by Kosaka Laboratory Ltd.
• the conditions are as follows, and the average value of three measurements was used as the value.
• Stylus tip radius ⁇ 0.5
• Urethane-based two-component effect adhesive (“Takelac (registered trademark) 5253” and “Takenate (registered trademark) 8 50” manufactured by Mitsui Chemicals, Inc. on the side of the polyester film at 13.5: 1 (weight ratio )), and a non-stretched polypropylene film (“1 1 47” manufactured by Toyobo Co., Ltd.) with a thickness of 70 is bonded as a heat-sealable resin layer by a dry lamination method at 40° ⁇ .
• a laminate film (laminate) was obtained by aging for 4 days. Note that the thickness of the adhesive layer formed of the urethane-based two-component curing type adhesive after drying was about 4 squares in all cases.
• the obtained water-filled 4-side sealed bag was immersed in hot water at 130°C for 30 minutes to obtain a retort-treated bag.
• a sealant heat-sealable resin layer
• the puncture resistance is It depends only on the laminating strength on the face side and not on the laminating strength on the face side.
• the laminating strength on the face side is lower than the laminating strength on the face side, so if the bag in which the face sides of the polyester film are bonded together with a sealant is good
• a bag in which the faces of polyester films are bonded together with a sealant provides good bag breakage resistance.
• the bag-breaking resistance was evaluated only for the bag in which the face surfaces of the polyester film were bonded together via the sealant.
• the bag filled with the above-mentioned retort-treated water was placed at a room temperature of 5° and a relative humidity of 35% at a height of 100°.
• the surface of the bag was dropped onto the concrete plate from position 10 and dropped 10 times, and the percentage of bags that did not tear when dropped in the horizontal direction was calculated.
• the surface of the bag was made to fall vertically and dropped 10 times, and the percentage of bags that did not tear when dropped in the vertical direction was calculated.
• the number of bags used in the test was 20 in both the horizontal and vertical directions.
• Laminate strength was measured using a 1-chome 1-500 model. Laminate strength has a pull rate of 20 11"
• the content of silica particles in the resin composition for producing the biaxially oriented polyester film is 0.16% by mass as the silica concentration.
• the obtained unstretched sheet was heated in the longitudinal direction (MD) at a temperature of 70°C to 3.
• Table 1 shows the resin composition of the polyester resin composition and the film forming conditions. In addition, Table 1 shows the physical properties of the obtained film and the evaluation results.
• a biaxially oriented polyester film having a thickness of 15 Mm was formed in the same manner as in Example 1 except that the resin composition of the polyester resin composition was changed as described in Table 1 in Example 1.
• Example 1 except that the temperature of the hot air on the face side and the face on the face side were changed in the heat setting treatment step, and the resin composition of the polyester resin composition and the film forming conditions were described in Table 1, as in Example 1.
• a biaxially oriented film was formed into a biaxially oriented polyester film having a thickness of 15. Table 1 shows the physical properties and the evaluation results of the obtained film.
• Example 1 except that the cold air was not blown from the face side by the multi-duct when the molten resin was brought into close contact with the cooling port, and the resin composition of the polyester resin composition and the film forming conditions were described in Table 1.
• a biaxially oriented film was formed in the same manner as in 1 to obtain a biaxially oriented polyester film having a thickness of 15.
• the obtained film had a large difference in crystallinity between the film surface and the Mitsumi surface, so the laminating strength was low, and the bag-breaking resistance after water leveling was poor.
• Example 1 a biaxially oriented film was formed in the same manner as in Example 1 except that the resin composition of the polyester resin composition was changed as described in Table 1, and a biaxially oriented polyester film having a thickness of 15 was formed. Obtained. Since the obtained film had a large difference in crystallinity between the film surface and the Mitsumi surface, the lami-strength was low and the horizontal bag drop resistance was poor.
• Example 1 except that the cold air was not blown from the face side by the multi-duct when the molten resin was brought into close contact with the cooling port, and the resin composition of the polyester resin composition and the film forming conditions were described in Table 1.
• a biaxially oriented film was formed in the same manner as in 1 to obtain a biaxially oriented polyester film having a thickness of 15.
• the obtained film has a large difference in crystallinity between the film surface and the Mitsumi surface, so that the lami-strength is low, the bag-breaking resistance to horizontal flattening is poor, and the stab strength is low and the piercing strength is low. Since it is low, the resistance to bag breakage during vertical drop was poor.
• Table 1 ⁇ 02020/175066 30 ((171?2020/004369
• Example 1 a biaxially oriented film was formed in the same manner as in Example 1 except that the resin composition of the polyester resin composition was described in Table 1 to obtain a biaxially oriented polyester film having a thickness of 15. Since the obtained film had a small proportion of Mitsuko, the piercing strength was low and the bag tearing resistance against vertical drop was poor. The results are shown in Table 1.
• the biaxially oriented polyester film of the present invention is mainly composed of Mending, and has excellent pinhole resistance and impact resistance, so that the bag produced by laminating it with the sealant film is difficult to tear.
• the conventional film mainly composed of Mingo has a large difference in surface roughness and laminating strength between the surface and the surface, but the film of the present invention has a small difference between the surface and the surface, and has excellent laminating strength on both surfaces. Therefore, it can be widely used as a base material for a packaging laminate having various layer structures.

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• 2019
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• 2020
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