WO2021200489A1 - 二軸延伸ポリアミドフィルム - Google Patents

二軸延伸ポリアミドフィルム Download PDF

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Publication number
WO2021200489A1
WO2021200489A1 PCT/JP2021/012304 JP2021012304W WO2021200489A1 WO 2021200489 A1 WO2021200489 A1 WO 2021200489A1 JP 2021012304 W JP2021012304 W JP 2021012304W WO 2021200489 A1 WO2021200489 A1 WO 2021200489A1
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WIPO (PCT)
Prior art keywords
film
layer
polyamide
biaxially stretched
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/012304
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和茂 上田
考道 後藤
卓郎 遠藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to US17/906,313 priority Critical patent/US12391827B2/en
Priority to KR1020227034986A priority patent/KR20220160603A/ko
Priority to CN202180019647.7A priority patent/CN115243892B/zh
Priority to EP21778793.6A priority patent/EP4129674A4/en
Priority to JP2022512031A priority patent/JP7708093B2/ja
Publication of WO2021200489A1 publication Critical patent/WO2021200489A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B32B2307/414—Translucent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/581—Resistant to cut
    • 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
    • B32B2377/00—Polyamides
    • 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
    • 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
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a biaxially stretched polyamide film having excellent impact resistance, bending pinhole resistance, and friction pinhole resistance.
  • the biaxially stretched polyamide film of the present invention is suitably used for food packaging films and the like.
  • a biaxially stretched film made of an aliphatic polyamide typified by polyamide 6 has excellent impact resistance and bending pinhole resistance, and is widely used as various packaging material films.
  • a film in which a polyamide-based elastomer is mixed with an aliphatic polyamide is known as a means for improving the above-mentioned bending pinhole resistance (see, for example, Patent Document 1).
  • This film has good bending pinhole resistance and impact resistance in a low temperature environment, and pinholes due to bending fatigue are unlikely to occur even in a low temperature environment.
  • the polyamide-based elastomer added during film production is thermally deteriorated, so that a deteriorated product called rheumatism is likely to be generated at the lip outlet of the die.
  • rheumatism is likely to be generated at the lip outlet of the die.
  • the deteriorated product itself drops to produce a defective product, which lowers the production efficiency during continuous film production.
  • Pinholes are generated not only by bending but also by friction (rubbing). Pinholes due to bending and methods for improving pinholes due to friction often conflict with each other. For example, when the flexibility of the film is increased, bending pinholes are less likely to occur, but the softening tends to cause pinholes due to friction.
  • a laminate for packaging that improves the occurrence of pinholes due to bending or friction by providing a surface coating agent on the outer surface of the biaxially stretched polyamide film has been proposed (see, for example, Patent Document 2). However, this method has little effect of preventing the occurrence of friction pinholes. In addition, a coating process is required.
  • Patent Documents 3 and 4 disclose a stretched film made of a polyamide-based resin composition containing 1 to 10% by mass of a polyester-based thermoplastic elastomer. According to such a technique, it is excellent in bending resistance even in a low temperature environment, but even in these techniques, since an elastomer component having low heat resistance is present on the surface layer, deterioration called rheumatism is performed at the lip outlet of the die. There was still room for improvement in the problem of easy production.
  • Japanese Unexamined Patent Publication No. 11-254615 Japanese Unexamined Patent Publication No. 2001-205761 International Publication No. 2019/131752 Japanese Unexamined Patent Publication No. 2019-147964 Japanese Unexamined Patent Publication No. 10-29264
  • An object of the present invention is to have excellent pinhole resistance due to bending and pinhole resistance due to repeated contact, excellent puncture resistance, and a biaxial structure capable of suppressing the generation of foreign matter during film formation. It is to provide a stretched polyamide film. Further, in addition to the above, an easily adhesive polyamide film having excellent water-resistant adhesive strength with a sealant film and capable of suppressing the generation of foreign substances during film formation, or a biaxially stretched polyamide film having excellent gas barrier properties is provided. It is to be.
  • the present invention has the following configuration.
  • a biaxially stretched polyamide film in which a functional layer (B layer) is laminated on at least one side of a base material layer (A layer), and the base material layer (A layer) is at least (a) polyamide 6 resin 70 to.
  • Biaxial stretching characterized by containing 99% by mass and (b) 1 to 20% by mass of an aliphatic or aromatic aliphatic polyester resin, and the functional layer (B layer) containing at least 70% by mass of a polyamide 6 resin.
  • the (b) aliphatic or aromatic aliphatic polyester resin is at least one polyester resin selected from the group consisting of polybutylene succinate, polybutylene succinate adipate, and polybutylene adipate terephthalate.
  • the polyamide resin from which at least a part of the raw material is derived from biomass is at least one type of polyamide resin selected from the group consisting of polyamide 11, polyamide 410, polyamide 610, and polyamide 1010 [].
  • the biaxially stretched polyamide film according to. [5] The biaxially stretched polyamide film (a) Gelboflex according to any one of [1] to [4], wherein the biaxially stretched polyamide film satisfies the following (a) to (c).
  • the number of bending fatigue pinholes when the bending test using a tester is performed 1000 times at a temperature of 1 ° C. is 5 or less.
  • Strength is 0.67 N / ⁇ m or more
  • the biaxially stretched polyamide film of the present invention contains a polyamide 6 resin as a main component, and by arranging a layer in which a specific polyester resin is blended in the inner layer of the film, impact resistance, bending resistance, pinhole resistance, and friction resistance pins are provided. Excellent hole property.
  • the elastomer component does not deteriorate inside the die in the film forming process of the film, it is possible to suppress the adhesion of deteriorated substances to the inner surface of the die and the adhesion of rheumatism to the die slip outlet for a long time. It is possible to suppress the thickness unevenness of the film caused by the adhesion of deteriorated substances to the inner surface of the die and the outlet of the die slip. Further, since the number of times of stopping the production and cleaning the lip of the die can be reduced, the biaxially stretched polyamide film of the present invention enables continuous production for a long time.
  • the biaxially stretched polyamide film of the present invention is a biaxially stretched polyamide film in which a functional layer (B) is laminated on at least one side of a layer A (base material layer). The details of each layer will be described below.
  • the base material layer (A layer) is composed of a resin composition containing at least (a) 70 to 99% by mass of a polyamide 6 resin and (b) 1 to 20% by mass of an aliphatic or aromatic aliphatic polyester resin.
  • a biaxially stretched polyamide film having excellent mechanical strength such as impact strength and gas barrier property such as oxygen can be obtained.
  • the polyamide 6 used for the base material layer (layer A) is usually produced by ring-opening polymerization of ⁇ -caprolactam.
  • the polyamide 6 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
  • the relative viscosity of the polyamide 6 is preferably 1.8 to 4.5, more preferably 2.6 to 3.2. If the relative viscosity is less than 1.8, the impact strength of the film is insufficient. If it is larger than 4.5, the load on the extruder becomes large and it becomes difficult to obtain an unstretched film before stretching.
  • a biaxially stretched polyamide film having excellent bending pinhole resistance By containing 1 to 20% by mass of an aliphatic or aromatic aliphatic polyester resin in the base material layer (layer A), a biaxially stretched polyamide film having excellent bending pinhole resistance can be obtained.
  • the aliphatic or aromatic aliphatic polyester resin contained in the base material layer (layer A) preferably has a glass transition temperature (Tg) of -30 ° C or lower.
  • Tg glass transition temperature
  • polybutylene succinate and polybutylene succinate adipate are preferable as the preferred aliphatic polyester resin
  • polybutylene adipate terephthalate is preferable as the aromatic aliphatic polyester resin because they have flexible properties.
  • the lower limit of the aliphatic or aromatic aliphatic polyester resin contained in the base material layer (layer A) is preferably 1% by mass, more preferably 2% by mass, and most preferably 3% by mass. If the amount of the aliphatic or aromatic aliphatic polyester resin added to the base material layer (layer A) is less than 1% by mass, the effect of improving the bending pinhole resistance cannot be obtained.
  • the upper limit of the aliphatic or aromatic aliphatic polyester resin contained in the base material layer (layer A) is preferably 20% by mass, more preferably 15% by mass.
  • the amount of the aliphatic or aromatic aliphatic polyester resin added to the base material layer (layer A) exceeds 20% by mass, the film becomes too soft, and not only the piercing strength and the impact strength are lowered, but also the film becomes Since it is easy to stretch, pitch deviation is likely to occur during processing such as printing.
  • the base material layer (layer A) can further improve the bending pinhole resistance by further containing a specific polyamide resin containing a raw material derived from biomass.
  • the upper limit of the content of the polyamide resin in which at least a part of the raw material contained in the base material layer (A layer) is derived from biomass is preferably 30% by mass, more preferably 20% by mass. If the content of the polyamide resin in which at least a part of the raw material is derived from biomass exceeds 30% by mass, the molten film becomes unstable when casting the molten film, and it becomes difficult to obtain a homogeneous unstretched film.
  • polyamide resin in which at least a part of the raw material that can be used for the base material layer (A layer) is derived from biomass, polyamide 11, polyamide 610, polyamide 1010 and polyamide 410 are preferable in terms of availability.
  • the polyamide 11 is a polyamide resin having a structure in which a monomer having 11 carbon atoms is bonded via an amide bond.
  • Polyamide 11 is usually obtained by using aminoundecanoic acid or undecanelactam as a monomer.
  • aminoundecanoic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutrality).
  • the structural unit derived from these monomers having 11 carbon atoms is preferably 50% or more, and may be 100%, of all the structural units in the polyamide 11.
  • the polyamide 11 is usually produced by the ring-opening polymerization of the above-mentioned undecane lactam.
  • the polyamide 11 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
  • the relative viscosity of the polyamide 11 is preferably 1.8 to 4.5, more preferably 2.4 to 3.2. If the relative viscosity is less than 1.8, the impact strength of the film is insufficient. If it is larger than 4.5, the load on the extruder becomes large and it becomes difficult to obtain an unstretched film before stretching.
  • the polyamide 610 is a polyamide resin having a structure in which a monomer having 6 carbon atoms and a monomer having 10 carbon atoms are bonded via an amide bond.
  • polyamide 610 is obtained by copolymerization of diamine and dicarboxylic acid, and hexamethylenediamine and sebacic acid are used, respectively.
  • sebacic acid is a monomer obtained from castor oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutrality).
  • the total of the structural units derived from the monomer having 6 carbon atoms and the structural units derived from the monomer having 10 carbon atoms is 50 out of all the structural units in the polyamide 610. It is preferably% or more, and may be 100%.
  • the above-mentioned polyamide 1010 is a polyamide resin having a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are copolymerized.
  • 1,10-decanediamine (decamethylenediamine) and sebacic acid are used for the polyamide 1010.
  • Decamethylenediamine and sebacic acid are monomers obtained from castor oil and are therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutrality).
  • the total of the structural units derived from diamine having 10 carbon atoms and the structural units derived from dicarboxylic acid having 10 carbon atoms is 50% or more of the total structural units in the polyamide 1010. It is preferably present, and may be 100%.
  • the above-mentioned polyamide 410 is a polyamide resin having a structure in which a monomer having 4 carbon atoms and a diamine having 10 carbon atoms are copolymerized.
  • sebacic acid and tetramethylenediamine are used for the polyamide 410.
  • the sebacic acid those using castor oil derived from vegetable oil as a raw material are preferable from the viewpoint of the environment.
  • the sebacic acid used here one obtained from castor oil is desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutrality).
  • the base material layer (layer A) requires various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents and antifogging agents, ultraviolet absorbers, dyes, and pigments. It can be contained accordingly.
  • the base material layer (layer A) may contain a thermoplastic resin other than the polyamide 6 resin as long as the object of the present invention is not impaired.
  • a thermoplastic resin other than polyamide for example, a polyester polymer such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, or a polyolefin polymer such as polyethylene or polypropylene may be contained. good.
  • the functional layer (B layer) is characterized by containing 70 to 100% by mass or more of the polyamide 6 resin.
  • the functional layer (B layer) contains 70% by mass or more of the polyamide 6 resin, a biaxially stretched polyamide film having excellent mechanical strength such as impact strength and gas barrier property such as oxygen can be obtained.
  • the polyamide 6 resin the same one as the polyamide 6 resin used in the base material layer (layer A) can be used.
  • various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents and antifogging agents, ultraviolet absorbers, dyes, pigments, etc. are applied to the functional layer (layer B). It can be contained according to the function provided on the surface of the layer B).
  • a soft resin such as a polyamide-based elastomer or a polyolefin-based elastomer or a substance that generates a large amount of voids. Not preferred.
  • the functional layer (B layer) may contain a thermoplastic resin in addition to the polyamide 6 resin as long as the object of the present invention is not impaired.
  • a thermoplastic resin such as polyamide MXD6 resin, polyamide 11 resin, polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, and polyamide 6/66 copolymer resin can be mentioned.
  • a thermoplastic resin other than polyamide for example, a polyester polymer such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, or a polyolefin polymer such as polyethylene or polypropylene may be contained. good.
  • the functional layer (B layer) preferably contains fine particles, an organic lubricant, or the like as a lubricant in order to improve the slipperiness of the film.
  • the fine particles can be appropriately selected from inorganic fine particles such as silica, kaolin and zeolite, and polymer organic fine particles such as acrylic and polystyrene. From the viewpoint of transparency and slipperiness, it is preferable to use silica fine particles.
  • the average particle size of the fine particles is preferably 0.5 to 5.0 ⁇ m, more preferably 1.0 to 3.0 ⁇ m. If the average particle size is less than 0.5 ⁇ m, a large amount of addition is required to obtain good slipperiness. On the other hand, if it exceeds 5.0 ⁇ m, the surface roughness of the film tends to be too large and the appearance tends to be deteriorated.
  • the range of the pore volume of silica is preferably 0.5 to 2.0 ml / g, and more preferably 0.8 to 1.6 ml / g. If the pore volume is less than 0.5 ml / g, voids are likely to occur and the transparency of the film deteriorates. When the pore volume exceeds 2.0 ml / g, surface protrusions due to fine particles tend to be difficult to form.
  • fatty acid amide and / or fatty acid bisamide can be contained.
  • the fatty acid amide and / or the fatty acid bisamide include erucic acid amide, stearic acid amide, ethylene bisstearic acid amide, ethylene bisbehenic acid amide, and ethylene bisoleic acid amide.
  • the content of the fatty acid amide and / or the fatty acid bisamide added to the functional layer (B layer) is preferably 0.01 to 0.40% by mass, and more preferably 0.05 to 0.30% by mass.
  • the functional layer (B layer) is a polyamide resin other than polyamide 6 for the purpose of improving the slipperiness of the film, for example, polyamide MXD6 resin, polyamide 11, polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin. , Polyamide 6.66 copolymer resin and the like can be added.
  • polyamide MXD6 resin is preferable, and 1 to 10% by mass is preferably added. If it is less than 1% by mass, the effect of improving the slipperiness of the film is small. If it is more than 10% by mass, the slipperiness improving effect of the film is saturated.
  • Polyamide MXD6 resin is produced by polycondensation of metaxylylenediamine and adipic acid.
  • the relative viscosity of the polyamide MXD6 is preferably 1.8 to 4.5, more preferably 2.0 to 3.2. If the relative viscosity is less than 1.8 or greater than 4.5, it may be difficult to knead with the polyamide resin in the extruder.
  • a polyamide resin other than polyamide 6 can be added to the functional layer (layer B) for the purpose of improving adhesiveness.
  • a copolymerized polyamide resin such as a polyamide 6/12 copolymer resin and a polyamide 6/66 copolymer resin is preferable.
  • Examples of the method of adding auxiliary materials and additives such as lubricants and antioxidants to the base material layer (A layer) and the functional layer (B layer) of the biaxially stretched polyamide film of the present invention include resin polymerization and an extruder. It can be added at the time of melt extrusion in. A high concentration masterbatch may be prepared and the masterbatch may be added to the polyamide resin during film production. This can be done by such a known method.
  • the thickness of the biaxially stretched polyamide film of the present invention is not particularly limited, but when used as a packaging material, it is usually 100 ⁇ m or less, and generally 5 to 50 ⁇ m thick is used, and particularly 8 to 8 to 50 ⁇ m. The one of 30 ⁇ m is used.
  • the thickness of the base material layer (A layer) is preferably 50 to 93%, particularly 60 to 93% of the total thickness of the base material layer (A layer) and the functional layer (B layer). ..
  • the content of carbon derived from biomass as measured by upper radioactive carbon (C14) becomes the total carbon in the polyamide film.
  • it is preferably contained in an amount of 1 to 15%.
  • the biaxially stretched polyamide film of the present invention has 5 or less pinhole defects when a twist bending test using a gelboflex tester according to the measurement method described in the examples is carried out 1000 times at a temperature of 1 ° C. More preferably, the number is 3 or less. The smaller the number of pinhole defects after the bending test, the better the bending pinhole resistance. If the number of pinholes is 5 or less, pinholes are less likely to occur even if the packaging bag is loaded during transportation. A packaging bag is obtained.
  • the biaxially stretched polyamide film of the present invention has a friction-resistant pinhole test according to the measurement method described in the examples, and the distance to the occurrence of pinholes is 2900 cm or more. It is more preferably 3100 cm or more, still more preferably 3300 cm or more. The longer the distance where pinholes occur, the better the resistance to friction pinholes. If the distance where pinholes occur is 2900 cm or more, pinholes will occur even if the packaging bag rubs against a cardboard box during transportation. A packaging bag that is difficult to obtain can be obtained.
  • the biaxially stretched polyamide film of the present invention is characterized in that it is excellent in both the above-mentioned bending-resistant pinhole resistance and friction-resistant pinhole resistance.
  • the biaxially stretched polyamide film of the present invention having these characteristics is extremely useful as a packaging film because pinholes are less likely to occur during transportation.
  • the film of the present invention has a heat shrinkage rate at 160 ° C. for 10 minutes in the range of 0.6 to 3.0% in both the flow direction (hereinafter abbreviated as MD direction) and the width direction (hereinafter abbreviated as TD direction). It is preferably, more preferably 0.6 to 2.5%. If the heat shrinkage rate exceeds 3.0%, curling or shrinkage may occur when heat is applied in the next process such as laminating or printing. In addition, the lamination strength with the sealant film may be weakened. Although it is possible to set the heat shrinkage rate to less than 0.6%, it may become mechanically brittle. In addition, productivity may deteriorate.
  • the impact strength of the biaxially stretched polyamide film of the present invention is preferably 0.7 J / 15 ⁇ m or more.
  • a more preferable impact strength is 0.9 J / 15 ⁇ m or more.
  • the piercing strength of the film of the present invention is preferably 0.67 N / ⁇ m or more.
  • the piercing strength of the film of the present invention is preferably 0.67 N / ⁇ m or more.
  • the haze value of the biaxially stretched polyamide film of the present invention is preferably 10% or less. It is more preferably 7% or less, still more preferably 5% or less. When the haze value is small, the transparency and gloss are good, so when used in a packaging bag, it can print beautifully and increase the commercial value. Since the haze value increases when fine particles are added to improve the slipperiness of the film, the haze value can be reduced by putting the fine particles only in the functional layer (B layer) of the surface layer.
  • the biaxially stretched polyamide film of the present invention preferably has a lamination strength of 4.0 N / 15 mm or more after being bonded to the polyethylene-based sealant film described in Examples.
  • the biaxially stretched polyamide film is usually laminated with a sealant film and then processed into a packaging bag.
  • the above-mentioned lamination strength is 4.0 N / 15 mm or more
  • sufficient strength of the seal portion can be obtained when a packaging bag is produced using the biaxially stretched polyamide film of the present invention in various laminated configurations.
  • a packaging bag that is hard to tear can be obtained.
  • the biaxially stretched polyamide film of the present invention can be subjected to corona treatment, coating treatment, flame treatment and the like.
  • the biaxially stretched polyamide film of the present invention can be produced by a known production method.
  • a sequential biaxial stretching method and a simultaneous biaxial stretching method can be mentioned.
  • the sequential biaxial stretching method is preferable because the film forming speed can be increased and it is advantageous in terms of manufacturing cost.
  • the raw material resin is melt-extruded using an extruder, extruded into a film from a T-die, cast on a cooling roll and cooled to obtain an unstretched film.
  • a coextrusion method using a feed block, a multi-manifold, or the like is preferable.
  • a dry laminating method, an extrusion laminating method, or the like can also be selected.
  • the polyamide resin composition used for the base material layer (A layer) and the functional layer (B layer) has a difference in melt viscosity between the base material layer (A layer) and the functional layer (B layer). It is desirable to reduce the amount.
  • the melting temperature of the resin is preferably 220 to 350 ° C. If it is less than the above, unmelted matter or the like may be generated, and appearance defects such as defects may occur. If it exceeds the above, deterioration of the resin or the like may be observed, and molecular weight or appearance may be deteriorated.
  • the die temperature is preferably 250 to 350 ° C.
  • the cooling roll temperature is preferably ⁇ 30 to 80 ° C., more preferably 0 to 50 ° C.
  • a method using an air knife or an electrostatic adhesion method for imprinting an electrostatic charge is preferably applied. can.
  • the latter is preferably used. It is also preferable to cool the opposite surface of the cooling roll of the cast unstretched film. For example, it is preferable to use a method of bringing the cooling liquid in the tank into contact with the opposite surface of the cooling roll of the unstretched film, a method of applying a liquid that evaporates with a spray nozzle, a method of spraying a high-speed fluid to cool the film, and the like. ..
  • the unstretched film thus obtained is stretched in the biaxial direction to obtain the biaxially stretched polyamide film of the present invention.
  • the stretching method may be either a simultaneous biaxial stretching method or a sequential biaxial stretching method.
  • the sequential biaxial stretching method is preferable because the film forming speed can be increased and it is advantageous in terms of manufacturing cost.
  • multi-step stretching such as one-step stretching or two-step stretching can be used.
  • multi-stage stretching in the MD direction such as two-stage stretching, is preferable in terms of physical properties and uniformity (isotropy) of physical properties in the MD and TD directions, rather than one-stage stretching.
  • Roll stretching is preferable for stretching in the MD direction in the sequential biaxial stretching method.
  • the lower limit of the stretching temperature in the MD direction is preferably 50 ° C., more preferably 55 ° C., and even more preferably 60 ° C. If the temperature is lower than 50 ° C., the resin does not soften and stretching may be difficult.
  • the upper limit of the stretching temperature in the MD direction is preferably 120 ° C., more preferably 115 ° C., and even more preferably 110 ° C. If the temperature exceeds 120 ° C., the resin may become too soft and stable stretching may not be possible.
  • the lower limit of the stretching ratio in the MD direction is preferably 2.2 times, more preferably 2.5 times, and further preferably 2. It is eight times. If it is less than 2.2 times, the thickness accuracy in the MD direction is lowered, and the crystallinity is too low, so that the impact strength may be lowered.
  • the upper limit of the draw ratio in the MD direction is preferably 5.0 times, more preferably 4.5 times, and most preferably 4.0 times. If it exceeds 5.0 times, subsequent stretching may be difficult.
  • the stretching in the MD direction is performed in multiple stages, the stretching as described above is possible in each stretching, but the product of the stretching magnifications in all MD directions is 5.0 or less. It is necessary to adjust the draw ratio.
  • the first-stage stretching is preferably 1.5 to 2.1 times, and the second-stage stretching is preferably 1.5 to 1.8 times.
  • the film stretched in the MD direction is stretched in the TD direction with a tenter, heat-fixed, and relaxed (also referred to as relaxation treatment).
  • the lower limit of the stretching temperature in the TD direction is preferably 50 ° C., more preferably 55 ° C., and even more preferably 60 ° C. If the temperature is lower than 50 ° C., the resin does not soften and stretching may be difficult.
  • the upper limit of the stretching temperature in the TD direction is preferably 190 ° C., more preferably 185 ° C., and even more preferably 180 ° C. If it exceeds 190 ° C., it may crystallize and stretching may become difficult.
  • the lower limit of the draw ratio in the TD direction (in the case of multi-stage stretching, the total draw ratio multiplied by each magnification) is preferably 2.8, more preferably 3.2 times, still more preferably 3.5. It is double, and particularly preferably 3.8 times. If it is less than 2.8, the thickness accuracy in the TD direction is lowered, and the crystallinity is too low, so that the impact strength may be lowered.
  • the upper limit of the draw ratio in the TD direction is preferably 5.5 times, more preferably 5.0 times, still more preferably 4.7, particularly preferably 4.5, and most preferably 4. It is three times. If it exceeds 5.5 times, the productivity may decrease significantly.
  • the selection of the heat fixing temperature is an important factor in the present invention. As the heat fixing temperature is increased, the crystallization and orientation relaxation of the film progresses, the impact strength can be improved, and the heat shrinkage rate can be reduced. On the other hand, when the heat fixation temperature is low, crystallization and orientation relaxation are insufficient, and the heat shrinkage rate cannot be sufficiently reduced. Further, if the heat fixing temperature becomes too high, the resin deteriorates and the toughness of the film such as impact strength is rapidly lost.
  • the lower limit of the heat fixing temperature is preferably 210 ° C, more preferably 212 ° C.
  • the upper limit of the heat fixing temperature is preferably 220 ° C., more preferably 218 ° C. If the heat fixation temperature is too high, the impact strength tends to decrease.
  • the heat fixing time is preferably 0.5 to 20 seconds. Furthermore, it takes 1 to 15 seconds. The heat fixing time can be set to an appropriate time in consideration of the heat fixing temperature and the wind speed in the heat fixing zone. If the heat fixing conditions are too weak, crystallization and orientation relaxation will be insufficient, and the above problems will occur. If the heat fixing conditions are too strong, the toughness of the film will decrease.
  • the temperature for the relaxing treatment can be selected in the range from the heat fixing treatment temperature to the Tg of the resin, but the heat fixing treatment temperature is preferably ⁇ 10 ° C. to Tg + 10 ° C. If the relaxation temperature is too high, the contraction speed is too fast and causes distortion and the like, which is not preferable. On the contrary, if the relaxing temperature is too low, the relaxing treatment is not performed, the heat shrinkage is not lowered, and the dimensional stability is deteriorated.
  • the lower limit of the relaxation rate of the relaxation treatment is preferably 0.5%, more preferably 1%. If it is less than 0.5%, the heat shrinkage rate may not be sufficiently lowered.
  • the upper limit of the relaxation rate is preferably 20%, more preferably 15%, and even more preferably 10%. If it exceeds 20%, slack will occur in the tenter, which may make production difficult.
  • the biaxially stretched polyamide film of the present invention can be subjected to heat treatment or humidity control treatment in order to improve dimensional stability depending on the application.
  • heat treatment or humidity control treatment in order to improve dimensional stability depending on the application.
  • the coating layer (C) is a film having a coating layer (C) on at least one side of the biaxially stretched polyester film in order to impart easy adhesiveness to the film.
  • the coating layer (C) may contain one or more resins selected from the group consisting of polyester resin, polyurethane resin, polyacrylic resin and acrylic graft copolymerized polyester resin having a solid content of 0.01 to 3 g / m2. can.
  • the coating layer (C) is preferably provided by applying and drying a coating liquid before winding the film as a mill roll in the film manufacturing process.
  • the coating liquid can be applied to an unstretched film, a uniaxially stretched film, and / or a biaxially stretched film. When the film is sequentially produced by the biaxial stretching method, the coating liquid is usually applied to the uniaxially stretched film and dried. When the film is produced by simultaneous biaxial stretching, the coating liquid is usually applied to the non-axially stretched film and dried.
  • the coating liquid is applied and dried before winding the film as a mill roll in the film manufacturing process to provide a coating film. Therefore, the coating liquid is used to ensure safety and hygiene in manufacturing. , It is preferable to use an aqueous dispersion of resin.
  • a copolymerized polyester resin can be selected as the polyester resin.
  • the copolymerized polyester resin is a polycondensate of a dicarboxylic acid component, a diol component, and other ester-forming components.
  • Examples of the dicarboxylic acid component contained in the copolymerized polyester resin as a component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenylenedicarboxylic acid, 5-sodium sulfoisophthalic acid and the like.
  • Aromatic dicarboxylic acids such as succinic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid.
  • Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and tetrahydropyran acid can be mentioned.
  • 5-sulfoisophthalic acid In addition to the above dicarboxylic acid components, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,6-dicarboxylic acid, 5 (4-sulfophenoxy) are used to impart water dispersibility.
  • Isophthalic acid salts can be used. Of these, 5-sodium sulfoisophthalic acid is preferably used in the range of 1 to 10 mol%.
  • diol component contained in the copolymerized polyester resin examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and polyethylene glycol.
  • examples of the polyurethane resin include those obtained by reacting polyols having two or more active hydrogens with an organic polyisocyanate.
  • examples of the polyols include saturated polyester polyols; polyether polyols (for example, polyethylene glycol, polytetramethylene glycol, etc.); amino alcohols (for example, ethanolamine, diethanolamine, triethanolamine, etc.); unsaturated polyester polyols (for example, unsaturated polyester polyols).
  • unsaturated polyvalent carboxylic acid alone or a mixture of saturated polyvalent carboxylic acid and saturated polyhydric alcohols and a mixture of unsaturated polyhydric alcohols are polycondensed), polybutadiene polyols.
  • polybutadiene polyols for example, 1,2-polybutadiene polyol, 1,4-polybutadiene polyol, etc.
  • acrylic polyols variantous acrylic monomers and acrylic acid-based monomers having a hydroxyl group are copolymerized to have a hydroxyl group in the side chain.
  • Acrylic polyols and other polyols having an unsaturated double bond can be mentioned.
  • organic polyisocyanate examples include aromatic polyisocyanates (for example, diphenylmethane diisocyanate, toluene diisocyanate, etc.), aliphatic polyisocyanates (for example, hexamethylene diisocyanate, etc.), alicyclic polyisocyanates (for example, isophorone diisocyanate, etc.), and the like.
  • aromatic polyisocyanates for example, diphenylmethane diisocyanate, toluene diisocyanate, etc.
  • aliphatic polyisocyanates for example, hexamethylene diisocyanate, etc.
  • alicyclic polyisocyanates for example, isophorone diisocyanate, etc.
  • examples thereof include aromatic / aliphatic polyisocyanates (for example, killylene diisocyanate), and polyisocyanates obtained by reacting these isocyanates with a low molecular weight polyol in advance.
  • ⁇ Polyacrylic resin used for coating layer> examples of the polyacrylic resin include acrylic polymers obtained by polymerizing acrylic acid or methacrylic acid, or salts or esters thereof.
  • examples of the acrylate-based and methacrylic acid ester-based monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, and methyl methacrylate.
  • acrylic acid-based monomers such as acrylamide, methacrylamide, aminoethyl methacrylate, aminomethyl methacrylate, N-methylolacrylamide, and N-methoxymethylacrylamide may be added.
  • the acrylic polymer contains hydrophilic components such as an acrylic acid salt component, a methacrylic acid salt component, an acrylic acid component, an acrylamide component, a 2-hydroxyethyl acrylate component, and an N-methylol acrylamide component as a copolymerization component. It is preferable to enhance the functionality of the coating film. Further, it may be a copolymer having a functional group in the molecular side chain.
  • this acrylic polymer can also be obtained by using a hard component such as methyl methacrylate or ethyl methacrylate as a main component and copolymerizing a soft component such as an acrylic acid ester as a copolymerization component.
  • a hard component such as methyl methacrylate or ethyl methacrylate
  • a soft component such as an acrylic acid ester
  • An acrylic graft copolymerized polyester resin can be used as the coating layer (C), and in the present invention, an acrylic graft copolymerized polyester aqueous dispersion is a preferable example. It contains particles of grafted polyester and water, an aqueous solvent or an organic solvent, and has a translucent to milky white appearance.
  • This grafted polyester has a main chain made of polyester and a graft portion (side chain) formed by a polymer of a radically polymerizable monomer containing a radically polymerizable monomer having a hydrophilic group.
  • the average particle size of the grafted polyester particles in the acrylic graft copolymerized polyester aqueous dispersion measured by the laser light scattering method is 500 nm or less, preferably 10 nm to 500 nm, and more preferably 10 nm to 300 nm. If the average particle size exceeds 500 nm, the strength of the coating film after coating decreases.
  • the content of the acrylic graft copolymerized polyester particles in the acrylic graft copolymerized polyester aqueous dispersion is usually 1% by mass to 50% by mass, preferably 3% by mass to 30% by mass.
  • the particles in the acrylic graft copolymerized polyester aqueous dispersion that can be used in the present invention can have a core-shell structure having a polyester main chain as a core in an aqueous dispersion medium.
  • the coating film obtained from the above-mentioned acrylic graft copolymerized polyester aqueous dispersion has excellent adhesiveness to the polyamide film. Furthermore, since it has very excellent blocking resistance, it can be used without problems even on a film substrate having a relatively low glass transition point. Further, in the case of a laminated body, the adhesiveness with the adhesive used when laminating the printing ink or the sealant layer is also very good.
  • the obtained laminated film (also referred to as a laminated film) can be significantly improved in durability in retort treatment and boiling water treatment. Further, when a flexible grafted polyester having a glass transition temperature of the grafted polyester in the copolymerized polyester aqueous dispersion of 30 ° C. or lower, preferably 10 ° C. or lower is used, the durability of the laminate is further improved.
  • the polyester that can be used as the main chain of the grafted polyester in the present invention is preferably a saturated or unsaturated polyester synthesized from at least a dicarboxylic acid component and a diol component, and the obtained polyester is one kind of polymer or 2 It can be a mixture of polymers of more than one species. And polyester which is originally not dispersed or dissolved in water by itself is preferable.
  • the weight average molecular weight of the polyester that can be used in the present invention is 5000 to 10000, preferably 5000 to 50000. If the weight average molecular weight is less than 5000, the physical properties of the coating film such as post-processability of the dry coating film deteriorate.
  • the polyester itself as the main chain is easily solubilized, so that the grafted polyester to be formed cannot form the core-shell structure described later. If the weight average molecular weight of polyester exceeds 100,000, water dispersion becomes difficult. From the viewpoint of water dispersion, 100,000 or less is preferable.
  • the glass transition point is 30 ° C. or lower, preferably 10 ° C. or lower.
  • the dicarboxylic acid component includes at least one aromatic dicarboxylic acid, at least one aliphatic and / or alicyclic dicarboxylic acid, and at least one dicarboxylic acid having a radically polymerizable unsaturated double bond.
  • a mixture of dicarboxylic acids is preferable.
  • the aromatic dicarboxylic acid terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like can be used.
  • sodium 5-sulfoisophthalate may be used if desired.
  • aliphatic dicarboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, dimer acid, acid anhydrides thereof and the like can be used.
  • alicyclic dicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, acid anhydrides thereof and the like can be used.
  • dicarboxylic acid containing a radically polymerizable unsaturated double bond examples include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and a fat containing an unsaturated double bond as ⁇ , ⁇ -unsaturated dicarboxylic acids.
  • cyclic dicarboxylic acid 2,5-norbornenedicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like can be used.
  • fumaric acid, maleic acid and 2,5-norbornenedicarboxylic acid endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid
  • the diol component comprises at least one of an aliphatic glycol having 2 to 10 carbon atoms, an alicyclic glycol having 6 to 12 carbon atoms, and an ether bond-containing glycol.
  • aliphatic glycols having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6.
  • -Hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol and the like can be used.
  • 1,4-cyclohexanedimethanol or the like can be used as the alicyclic glycol having 6 to 12 carbon atoms.
  • the ether bond-containing glycol include glycols obtained by adding 1 to several mols of ethylene oxide or propylene oxide to each of two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and bisphenols, for example, 2,2. -Bis (4-hydroxyethoxyphenyl) propane or the like can be used.
  • Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may also be used as needed.
  • a trifunctional or higher functional polycarboxylic acid and / or polyol can be copolymerized.
  • trifunctional or higher functional polycarboxylic acids include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethyleneglucolbis (anhydrotrimeritate), and glycerol tris (anhydro). Hydrotrimeritate) and the like can be used.
  • trifunctional or higher functional polyol glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like can be used.
  • the trifunctional or higher functional polycarboxylic acid and / or polyol is 0 to 5 mol%, preferably 0 to 3 mol%, based on the total polycarboxylic acid component containing the dicarboxylic acid component or the total polyol component containing the diol component. Can be used in the range of.
  • the graft portion of the grafted polyester that can be used in the present invention is a monomer mixture containing at least one radically polymerizable monomer having a hydrophilic group or having a group that can be changed to a hydrophilic group later. It can be a polymer of origin.
  • the weight average molecular weight of the polymer constituting the graft portion is 500 to 50,000, preferably 4000 to 50,000.
  • the graft portion forms a hydrated layer of dispersed particles. In order to allow the particles to have a hydrated layer having a sufficient thickness and to obtain a stable dispersion, it is desirable that the weight average molecule of the graft portion derived from the radically polymerizable monomer is 500 or more.
  • the upper limit of the weight average molecular weight of the graft portion of the radically polymerizable monomer is preferably 50,000 as described above in terms of polymerizability in solution polymerization.
  • the amount of the polymerization initiator, the monomer dropping time, the polymerization time, the reaction solvent, and the monomer composition are appropriately selected, and a chain transfer agent or a polymerization inhibitor is appropriately combined as necessary. Get it done.
  • the glass transition point is 30 ° C or lower, preferably 10 ° C or lower.
  • hydrophilic group of the radically polymerizable monomer a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, a quaternary ammonium salt, a phosphoric acid group or the like can be used.
  • a group that can be changed to a hydrophilic group an acid anhydride, glycidyl, chlor or the like can be used.
  • the hydrophilicity introduced into the polyester by grafting can control the dispersibility of the grafted polyester in water.
  • the carboxyl group can accurately determine the amount to be introduced into the grafted polyester using an acid value known in the art, and thus controls the dispersibility of the grafted polyester in water. It is preferable to do so.
  • carboxyl group-containing radically polymerizable monomer examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid, and maleic anhydride which easily generates carboxylic acid in contact with water / amine.
  • a product, itaconic acid anhydride, methacrylic acid anhydride and the like can be used.
  • Preferred carboxyl group-containing radically polymerizable monomers are acrylic acid anhydride, methacrylic acid anhydride and maleic anhydride.
  • hydrophilic group-containing radical polymerizable monomer it is preferable to copolymerize at least one hydrophilic group-free radical polymerizable monomer.
  • hydrophilic group-containing monomer grafting to the polyester main chain does not occur smoothly, and it is difficult to obtain a good copolymerized polyester aqueous dispersion.
  • Highly efficient grafting can be achieved only by copolymerizing a radically polymerizable monomer that does not contain at least one hydrophilic group.
  • the radically polymerizable monomer containing no hydrophilic group one or more combinations of monomers having an ethylenically unsaturated bond and not containing a hydrophilic group as described above are used.
  • a monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and hydrokipropyl acrylate;
  • Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxylpropyl methacrylate; acrylamide , N-methylol acrylamide, diacetone acrylamide and
  • Vinyl compounds such as vinyl chloride, vinyl den, vinyl bromide, vinyl fluoride; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, t-butylstyrene, vinyltoluene, vinylnaphthalines; be able to. These monomers may be used alone or in combination of two or more.
  • the ratio of the hydrophilic group-containing monomer to the hydrophilic group-free monomer used is determined in consideration of the amount of the hydrophilic group introduced into the grafted polyester, but is usually determined by the mass ratio (hydrophilic group).
  • Containing monomer: a monomer containing no hydrophilic group) is in the range of 95: 5 to 5:95, preferably 90:10 to 10:90, and more preferably 80:20 to 40:60.
  • the total acid value of the grafted polyester is 600 to 4000 eq. / 10 6 g, preferably 700-3000 eq. / 10 6 g, most preferably 800-2500 eq. / 10 6 g.
  • the acid value is 600 eq.
  • the amount is 1/10 6 g or less, it is difficult to obtain a copolymerized polyester aqueous dispersion having a small particle size when the grafted polyester is dispersed in water, and the dispersion stability of the copolymerized polyester aqueous dispersion is further lowered.
  • the acid value is 4000 eq. When the amount is 1/10 6 g or more, the water resistance of the easy-adhesion layer formed from the copolymerized polyester aqueous dispersion becomes low.
  • the mass ratio (polyester: radically polymerizable monomer) of the polyester main chain to the graft portion in the acrylic graft copolymerized polyester is 40:60 to 95: 5, preferably 55:45 to 93: 7, and more preferably 60. : 40 to 90:10.
  • the mass ratio of the polyester main chain is 40% by mass or less, the excellent performance of the base polyester described above, that is, high processability, excellent water resistance, and excellent adhesion to various substrates can be sufficiently exhibited. On the contrary, it adds undesired performance of acrylic resin, that is, low workability, gloss, water resistance and the like.
  • the mass ratio of the polyester is 95% by mass or more, the amount of hydrophilic groups in the graft portion that imparts hydrophilicity to the grafted polyester is insufficient, and a good aqueous dispersion cannot be obtained.
  • the above coating liquid can be used as it is as a coating agent for forming a coating layer, but it is possible to impart a high degree of water resistance to the coating layer by further blending a cross-linking agent (curing resin) and performing curing.
  • a cross-linking agent curing resin
  • the cross-linking agent include phenol-formaldehyde resins obtained by condensing alkylated phenols, cresols and the like with formaldehyde; additions of urea, melamine, benzoguanamine and the like with formaldehyde, and alcohols having 1 to 6 carbon atoms with these additions.
  • An amino resin such as an alkyl ether compound composed of; a polyfunctional epoxy compound; a polyfunctional isocyanate compound; a blocked isocyanate compound; a polyfunctional aziridine compound; an oxazoline compound or the like can be used.
  • the coating layer used in the present invention may further contain additives such as an antistatic agent, an inorganic lubricant, and an organic lubricant in order to impart antistatic properties and slipperiness to the extent that the effects of the present invention are not impaired. can.
  • additives such as an antistatic agent, an inorganic lubricant, an organic lubricant or the like
  • an antistatic agent, an inorganic lubricant, an organic lubricant or the like is applied to the film surface, it is preferable to include these additives in the coating layer in order to prevent detachment of these additives.
  • a known coating method such as a gravure method, a reverse method, a die method, a bar method, or a dip method can be used.
  • the amount of the coating agent applied is 0.01 to 3 g / m 2 as a solid content with respect to the polyamide film after biaxial stretching. Preferably, it is applied so as to be 0.04 to 0.5 g / m 2.
  • the coating amount is 0.01 g / m 2 or less, sufficient adhesive strength between the coating layer and another layer cannot be obtained. If it exceeds 3 g / m 2 , blocking will occur, which is a problem in practical use.
  • the coating layer is formed by applying a coating agent to a biaxially stretched polyamide film base material, or applying a coating agent to an unstretched or uniaxially stretched polyamide film base material, then drying the coating layer, and further uniaxially stretching or, if necessary. It can be prepared by performing heat fixation after biaxial stretching.
  • the drying temperature after application of the coating agent is 150 ° C. or higher, preferably 200 ° C. or higher, to strengthen the coating film and improve the adhesiveness between the easy-adhesion layer and the polyamide film base material. ..
  • the biaxially stretched polyamide film of the present invention can be imparted with gas barrier properties by providing an inorganic thin film layer on at least one side of the film.
  • the inorganic thin film layer is a thin film made of a metal or an inorganic oxide.
  • the material for forming the inorganic thin film layer is not particularly limited as long as it can be made into a thin film, but from the viewpoint of transparency and gas barrier properties, silicon oxide (silica), aluminum oxide (alumina), a mixture of silicon oxide and aluminum oxide, etc.
  • the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% by mass of Al in terms of the mass ratio of the metal content. If the Al concentration is less than 20% by mass, the water vapor barrier property may be lowered. On the other hand, if it exceeds 70% by mass, the inorganic thin film layer tends to be hard, and the film may be destroyed during secondary processing such as printing or laminating, and the gas barrier property may be lowered.
  • the silicon oxide referred to here is various silicon oxides such as SiO and SiO 2 or a mixture thereof
  • aluminum oxide is various aluminum oxides such as AlO and A1 2 O 3 or a mixture thereof.
  • the film thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm. If the film thickness of the inorganic thin film layer is less than 1 nm, it may be difficult to obtain a satisfactory gas barrier property. On the other hand, even if the thickness exceeds 100 nm, the corresponding improvement effect of the gas barrier property can be obtained. This is not possible, and it is rather disadvantageous in terms of bending resistance and manufacturing cost.
  • the method for forming the inorganic thin film layer is not particularly limited, and is known, for example, a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • the method may be adopted as appropriate.
  • 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 SiO 2 and A1 2 O 3 or a mixture of SiO 2 and Al is preferably used as the vapor deposition raw material.
  • Particles are usually used as these vapor deposition raw materials, but at that time, it is desirable that the size of each particle is such that the pressure at the time of vapor deposition does not change, and the particle size is preferably 1 mm to 5 mm.
  • heating methods such as resistance heating, high frequency induction heating, electron beam heating, and laser heating can be adopted.
  • reactive vapor deposition using means such as introduction of oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor, ozone addition, ion assist, etc. as the reaction gas.
  • the film forming conditions can be arbitrarily changed, such as applying a bias to the film to be vapor-deposited (laminated film to be subjected to vapor deposition) and heating or cooling the film to be vapor-deposited.
  • a bias to the film to be vapor-deposited (laminated film to be subjected to vapor deposition) and heating or cooling the film to be vapor-deposited.
  • Such vapor deposition material, reaction gas, bias of the vapor deposition body, heating / cooling, and the like can be similarly changed when the sputtering method or the CVD method is adopted.
  • the biaxially stretched polyamide film of the present invention is processed into a laminated film in which a sealant film or the like is laminated, and then processed into a packaging bag.
  • the sealant film include an unstretched linear low density polyethylene (LLDPE) film, an unstretched polypropylene (CPP) film, and an ethylene-vinyl alcohol copolymer resin (EVOH) film.
  • Examples of the layer structure of the laminated film of the present invention include ONY / adhesive / LLDPE, ONY / adhesive / CPP, ONY / adhesive / Al / adhesive / CPP, ONY / adhesive / Al / adhesive.
  • Examples of the layer structure of the laminated film using the biaxially stretched polyamide film having the inorganic thin film layer (D) of the present invention include ONY / inorganic thin film layer / adhesive / CPP, PET / adhesive / ONY / inorganic.
  • the film was evaluated by the following measurement method. Unless otherwise specified, the measurement was carried out in a measurement room in an environment of 23 ° C. and 65% relative humidity.
  • a sample was obtained by cutting into strips of 15 mm in the direction perpendicular to the measurement direction.
  • a tensile test was carried out at a test speed of 200 mm / min using a tensile tester (AG-1 manufactured by Shimadzu Corporation) equipped with a 1 kN load cell and sample attachment.
  • the elastic modulus was calculated from the gradient of the obtained load-elongation curve. The measurement was performed with the number of samples 3, and the average value of each was calculated.
  • the obtained laminated film is cut into a cylinder of 12 inches x 8 inches to form a cylinder with a diameter of 3.5 inches, and one end of the cylindrical film is on the fixed head side of the Gelboflex tester and the other end is on the movable head side.
  • the initial gripping interval was 7 inches.
  • the first 3.5 inches of the stroke gives a 440 degree twist, then the 2.5 inches is subjected to flexion fatigue at a speed of 40 times / minute, such as finishing the entire stroke in a straight horizontal motion, and the laminated film.
  • the number of pinholes that occurred in was counted.
  • the measurement was performed in an environment of 1 ° C.
  • the test film was placed on a filter paper (Advantec, No.
  • Friction resistance of film Pinhole resistance Using a fastness tester (Toyo Seiki Seisakusho), a friction test was conducted by the following method, and the pinhole occurrence distance was measured.
  • a test sample similar to the one prepared in the above bending pinhole resistance evaluation was folded in four to prepare a test sample with sharp corners, and an amplitude: 25 cm, an amplitude speed: 30 times / with a fastness tester. Minutes, weight: 100 g weight, rubbed against the inner surface of the corrugated cardboard.
  • K280 ⁇ P180 ⁇ K210 (AF) (surface material liner ⁇ core material ⁇ back material liner (type of flute)) was used.
  • the pinhole occurrence distance was calculated according to the following procedure.
  • a friction test was performed with an amplitude of 100 times and a distance of 2500 cm.
  • the friction test was performed by increasing the number of amplitudes by 20 times and increasing the distance by 500 cm.
  • the friction test was performed by further increasing the number of amplitudes by 20 times and the distance by 500 cm. This was repeated and the distance at which the pinhole was opened was marked with a cross to make it level 1.
  • a friction test was performed by reducing the number of amplitudes of 20 times by a distance of 500 cm.
  • the friction test was performed by further reducing the number of amplitudes by 20 times and the distance by 500 cm. This was repeated and the distance at which the pinhole did not open was marked with a circle to make it level 1.
  • level 2 if the last was ⁇ at level 1, the number of amplitudes was increased 20 times and a friction test was performed. If the pinhole did not open, it was marked with ⁇ , and if it opened, it was marked with ⁇ . If the last was x at level 1, the number of amplitudes was reduced 20 times and a friction test was performed. If the pinhole did not open, a circle was added, and if the pinhole opened, a cross was added.
  • the level is 3 to 20
  • the previous level is ⁇
  • the number of amplitudes is increased 20 times and a friction test is performed. If the pinhole does not open, ⁇ is added, and if the pinhole opens, ⁇ is added. If it was x at the previous level, reduce the number of amplitudes by 20 times and perform a friction test. If the pinhole does not open, mark ⁇ , and if the pinhole opens, mark x. This is repeated, and levels 3 to 20 are marked with ⁇ or ⁇ . For example, the results shown in Table 1 were obtained. A method of obtaining the pinhole generation distance will be described using Table 1 as an example. Count the number of ⁇ and ⁇ tests for each distance.
  • the median is the distance with the most tests, and the coefficient is zero.
  • the coefficients are set to +1, +2, +3 ... Every 500 cm, and when the distance is short, the coefficients are set to -1, -2, -3 ... Every 500 cm.
  • the number of tests without holes and the number of tests with holes were compared, and the friction pinhole occurrence distance was calculated by each formula for the following cases A and B. ..
  • Friction pinhole generation distance median + 500 x ( ⁇ (coefficient x number of tests without holes) / hole Number of tests not opened) + 1/2)
  • Friction pinhole generation distance median + 500 x ( ⁇ (coefficient x number of tests with holes) / holes are opened Number of tests) -1 / 2)
  • Lamination strength with polyethylene-based sealant A laminate film produced in the same manner as described in the description of evaluation of bending pinhole resistance is cut into strips having a width of 15 mm and a length of 200 mm, and one end of the laminate film is cut into two. Peeled at the interface between the axially stretched polyamide film and the linear low-density polyethylene film, and used (manufactured by Shimadzu Corporation, Autograph) at a temperature of 23 ° C, a relative humidity of 50%, a tensile speed of 200 mm / min, and a peeling angle of 90 °. Under the above conditions, the lamination strength was measured three times in each of the MD direction and the TD direction, and evaluated by the average value.
  • Example 1-1 Using a device consisting of two extruders and a co-extruded T-die with a width of 380 mm, the layers are laminated in a structure of functional layer (B layer) / base material layer (A layer) / functional layer (B layer) by the feed block method.
  • the molten resin of the following resin composition was extruded from the T-die into a film, cast on a cooling roll whose temperature was adjusted to 20 ° C., and electrostatically adhered to obtain an unstretched film having a thickness of 200 ⁇ m.
  • the resin compositions of the base material layer (A layer) and the functional layer (B layer) are as follows.
  • Polyamide 6 manufactured by Toyo Boseki Co., Ltd., relative viscosity 2.8, melting point 220 ° C.
  • polybutylene terephthalate adipate manufactured by BASF, trade name " Ecoflex "
  • Resin composition constituting the functional layer (B layer) Polycarbonate 6 (manufactured by Toyo Boseki Co., Ltd., relative viscosity 2.8, melting point 220 ° C.) 95 parts by mass, and polyamide MXD6 (manufactured by Mitsubishi Gas Chemical Company Ltd., relative viscosity 2. 1.
  • the obtained unstretched film was guided to a roll-type stretcher, stretched 1.73 times in the MD direction at 80 ° C. using the difference in peripheral speed of the rolls, and then further stretched 1.85 times at 70 ° C. Subsequently, this uniaxially stretched film was continuously led to a tenter type stretching machine, preheated at 110 ° C., and then 1.2 times at 120 ° C., 1.7 times at 130 ° C., and 2.0 times at 160 ° C. in the TD direction.
  • Examples 1-2 to 1-11 The resin composition of the base material layer (A layer) and the functional layer (B layer), the film forming conditions such as the heat fixation temperature were changed as shown in Table 2, and a biaxially stretched film was obtained by the same method as in Example 1. rice field. Table 2 shows the evaluation results of the obtained biaxially stretched film.
  • -PBAT Polybutylene adipate terephthalate (BASF, Ecoflex)
  • PBS Polybutylene succinate (manufactured by Showa High Polymer Co., Ltd., Bionore 1001)
  • PBSA Polybutylene succinate adipate (manufactured by Showa High Polymer Co., Ltd., Bionore 3001)
  • -PAE Polyamide elastomer (manufactured by Arkema, nylon 12 / polytetramethylene glycol copolymer, Pebax SA01)
  • -PEE Maleic anhydride-modified polyester elastomer (manufactured by Mitsubishi Chemical Corporation, Tefablock)
  • Polyamide 11 (manufactured by Shuseisha, relative viscosity 2.5, melting point 186 ° C, biomass degree 100%)
  • Polyamide 410 (manufactured by DSM, ECOPaXX Q150-E, melting point 250 ° C., biomass degree 70%)
  • Polyamide 610 (manufactured by Arkema, RilsanS SMNO, melting point 222 ° C., biomass degree 63%)
  • Polyamide 1010 (manufactured by Arkema, RilsanT TMNO, melting point 202 ° C., biomass degree 100%)
  • the films of the examples were obtained with good both bending pinhole resistance and friction pinhole resistance.
  • the haze was low and the transparency was good, the impact strength and the piercing strength were strong, and the lamination strength with the sealant film was also high, which was excellent as a packaging film.
  • stable film formation was possible without any deteriorated substances adhering to the lip of the die.
  • Example 1 A biaxially stretched polyamide film was prepared in the same manner as in Example 1-1 according to the resin compositions and conditions shown in Table 3. The raw materials used in the resin composition are the same as in Example 1. For Comparative Example 1-5, a biaxially stretched polyamide film was produced by the following method.
  • Resin composition constituting the layer Polyamide 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220 ° C.) 97 parts by mass, and maleic anhydride-modified polyester elastomer (manufactured by Mitsubishi Chemical Co., Ltd., Primaloy AP GQ131) 3.0 Polyamide resin composition composed of parts by mass. Porous silica fine particles (manufactured by Fuji Silysia Chemical Ltd., average particle diameter 2.0 ⁇ m, pore volume 1.6 ml / g) 0.09 parts by mass. 300 ppm ethylene bisstearic acid amide.
  • the obtained unstretched film was longitudinally stretched 3.0 times by a roll stretching machine at 65 ° C., then laterally stretched 4.0 times by a tenter stretching machine having an atmosphere of 110 ° C., and further stretched at 210 ° C. by the same tenter.
  • a single-layer polyamide film having a thickness of 15 ⁇ m was prepared by heat treatment in the atmosphere of.
  • Table 3 shows the physical characteristics and various evaluation results of the biaxially stretched polyamide film produced in Comparative Example 1.
  • the biaxially stretched polyamide film containing no material for modifying the bending pinhole resistance of Comparative Example 1-1 was inferior in bending pinhole resistance.
  • Comparative Example 1-2 since there are too many materials for modifying the bending pinhole resistance, the bending pinhole resistance is excellent, but the haze value of the film is high, and the film impact strength, piercing strength, and friction pinhole resistance are also high.
  • Comparative Examples 1-3, 1-4 and 1-5 were inferior in friction pinhole property because the surface layer side also contained a material for modifying the bending pinhole resistance. In addition, deteriorated substances adhered to the lip of the die in the extrusion process.
  • Example 2 The biaxially stretched polyamide film prepared in Example 1-1 was used to prepare a laminate having the following configurations (1) to (9), and the laminates (1) to (9) were used on three sides. Seal type and pillow type packaging bags were produced. We were able to produce a packaging bag that has a good appearance and is not easily torn in a drop impact test.
  • Example 3 (Biaxially stretched polyamide film having a coating layer) Using a device consisting of two extruders and a co-extruded T-die with a width of 380 mm, the resin composition shown in Table 4 was subjected to a feed block method using a functional layer (B layer) / base material layer (A layer) / functional layer ( The molten resin was extruded into a film from the T-die by laminating in the structure of (B layer), cast on a cooling roll whose temperature was adjusted to 20 ° C., and electrostatically adhered to obtain an unstretched film having a thickness of 200 ⁇ m. The raw materials used in the resin composition are the same as in Example 1 and Comparative Example 1.
  • the obtained unstretched film was guided to a roll-type stretcher, stretched 1.73 times in the MD direction at 80 ° C. using the difference in peripheral speeds of the rolls, and then further stretched 1.85 times at 70 ° C.
  • the following coating liquid (A) was applied to this uniaxially stretched film with a roll coater, and then dried with warm air at 70 ° C.
  • This uniaxially stretched film was continuously guided to a tenter type stretcher, preheated at 110 ° C., and then stretched 1.2 times at 120 ° C., 1.7 times at 130 ° C., and 2.0 times at 160 ° C. in the TD direction. After heat-fixing treatment at 218 ° C., 7% relaxation treatment was performed at 218 ° C.
  • Example 3-4 the following coating liquid (B): an aqueous dispersion of polyurethane resin was used as the coating liquid.
  • Table 4 shows the physical characteristics and various evaluation results of the biaxially stretched polyamide film produced in Example 3.
  • the films of the examples were obtained with good both bending pinhole resistance and friction pinhole resistance.
  • the haze was low, the transparency was good, the impact strength and the piercing strength were strong, and the water-resistant lamination strength with the sealant film was also high, which was excellent as a packaging film.
  • stable film formation was possible without any deteriorated substances adhering to the lip of the die.
  • Example 3 A biaxially stretched polyamide film having a coating layer was prepared in the same manner as in Example 3 according to the resin compositions and conditions shown in Table 5.
  • a biaxially stretched polyamide film was produced by the following method. Using a device consisting of one extruder and a single-layer T-die with a width of 380 mm, the molten resin of the resin composition shown in Table 5 was extruded from the T-die into a film and cast on a cooling roll whose temperature was adjusted to 20 ° C. , An unstretched film having a thickness of 180 ⁇ m was obtained by electrostatically adhering. Next, the obtained unstretched film was longitudinally stretched 3.0 times in the MD direction by a roll-type stretching machine at 65 ° C.
  • the following coating liquid (A) was applied to this uniaxially stretched film with a roll coater, and then dried with warm air at 70 ° C.
  • This uniaxially stretched film is continuously led to a tenter type stretching machine, laterally stretched 4.0 times by a tenter stretching machine in an atmosphere of 110 ° C., and further heat-treated in an atmosphere of 210 ° C. by the same tenter to have a thickness of 15 ⁇ m.
  • a single-layer polyamide-based film was produced.
  • the composition obtained by NMR measurement and the like was as follows. ⁇ Dicarboxylic acid component terephthalic acid 48 mol% Isophthalic acid 48 mol% Fumaric acid 4 mol% ⁇ Diol component Neopentyl glycol 50 mol% Ethylene glycol 50 mol%
  • 75 parts by mass of the polyester resin, 56 parts by mass of methyl ethyl ketone and 19 parts by mass of isopropyl alcohol were placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a quantitative dropping device, and heated at 65 ° C. to stir to dissolve the resin. .. After the resin is completely dissolved, a solution prepared by dissolving a mixture of 17.5 parts by mass of methacrylic acid and 7.5 parts by mass of ethyl acrylate and 1.2 parts by mass of azobisdimethylvaleronitrile in 25 parts by mass of methyl ethyl ketone is 0.
  • the mixture was added dropwise to the polyester solution at 2 ml / min, and stirring was continued for another 2 hours after the addition was completed.
  • sampling 5 g
  • 300 parts by mass of water and 25 parts by mass of triethylamine were added to the reaction solution, and the mixture was stirred for 1 hour to prepare a dispersion of the grafted polyester.
  • the temperature of the obtained dispersion was raised to 100 ° C., and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a copolymerized polyester aqueous dispersion.
  • the obtained dispersion was white, had an average particle size of 300 nm, and had a B-type viscosity at 25 ° C. of 50 centipoise.
  • DSS was added and 125 MHz 13 C-NMR was measured.
  • the half width of the carbonyl carbon signal (160-175 ppm) of the polyester backbone was ⁇ (no signal detected), and the half width of the carbonyl carbon signal of methacrylic acid (181-186 ppm) in the graft portion was 110 Hz. ..
  • the solution sampled at the end of the grafting reaction was dried at 100 ° C.
  • the polyester graft efficiency was measured (NMR measurement), and the graft portion was hydrolyzed.
  • the molecular weight of was measured.
  • the acid value of the solid content is 2300 eq. It was / 10 6 g. 1
  • the molecular weight of the graft portion was a weight average molecular weight of 10000. Then, the aqueous dispersion obtained as described above was diluted with water so as to have a solid content concentration of 5% by mass to obtain a coating liquid (A).
  • 1,6-hexanediol was allowed to act to extend the chain, and an aminocarboxylic acid salt was reacted at the terminal to obtain a water-insoluble and water-dispersible polyurethane.
  • This was dispersed in hot water with stirring to obtain a 25% aqueous dispersion.
  • the aqueous dispersion of polyurethane was added to an equal amount mixture of ion-exchanged water and isopropyl alcohol so that the solid content was 5% by mass, and diluted to obtain a coating liquid (B).
  • Table 5 shows the physical characteristics and various evaluation results of the biaxially stretched polyamide film produced in Comparative Example 3.
  • the biaxially stretched polyamide film containing no material for modifying the bending pinhole resistance of Comparative Example 3-1 was inferior in bending pinhole resistance.
  • Comparative Example 3-2 since there are too many materials for modifying the bending pinhole resistance, the bending pinhole resistance is excellent, but the haze value of the film is high, and the film impact strength, puncture strength, and friction pinhole resistance are high. The sex was inferior.
  • Comparative Examples 3-3, 3-4 and 3-5 were inferior in friction pinhole property because the surface layer side also contained a material for modifying the bending pinhole resistance. In addition, deteriorated substances adhered to the lip of the die in the extrusion process.
  • Example 4 (Biaxially stretched polyamide film having an inorganic thin film layer)
  • the film-forming conditions such as the resin composition of the base material layer (A layer) and the functional layer (B layer) and the heat-fixing temperature were changed as shown in Table 6, and the biaxially stretched film was formed in the same manner as in Example 1-1.
  • Got The raw materials used in the resin composition are the same as in Example 1 and Comparative Example 1.
  • a composite oxide thin film layer of silicon dioxide and aluminum oxide was formed on the corona-treated surface of the obtained biaxially stretched polyamide film by the following method.
  • An inorganic thin film layer of a composite oxide of silicon dioxide and aluminum oxide was formed on the corona-treated surface of the obtained biaxially stretched polyamide film by an electron beam deposition method.
  • the film is set on the unwinding side of a continuous vacuum vapor deposition machine, and the film is wound by running through a cooling metal drum.
  • the pressure was reduced a continuous vacuum deposition apparatus below 10 @ -4 Torr, a deposition source from the lower portion of the cooling drum in an alumina crucible, granular SiO 2 of about 3 mm ⁇ 5 mm and (purity 99.9%) A1 2 O 3 (purity 99.9%) and was used.
  • the film thickness of the obtained inorganic thin film layer (SiO 2 / A1 2 O 3 composite oxide layer) was 13 nm.
  • Example 4-5 an inorganic thin film layer of aluminum oxide was formed as the inorganic thin film layer by the following method. ⁇ Formation of aluminum oxide (A1 2 O 3) inorganic thin layer> An inorganic thin film layer of aluminum oxide was formed on the corona-treated surface of the obtained biaxially stretched polyamide film by an electron beam deposition method. In the method of depositing aluminum oxide, the film is set on the unwinding side of a continuous vacuum vapor deposition machine, and the film is wound by running through a cooling metal drum.
  • the continuous vacuum deposition machine is depressurized to 10 -4 Torr or less, metallic aluminum having a purity of 99.99% is loaded into an alumina crucible from the lower part of the cooling drum, and the metallic aluminum is heated and evaporated into the vapor.
  • An aluminum oxide film having a thickness of 30 nm was formed by adhering and depositing on a film while supplying oxygen and causing an oxidation reaction.
  • Table 6 shows the physical characteristics and various evaluation results of the biaxially stretched polyamide film produced in Example 4.
  • Comparative Example 4 The resin composition of the base material layer (A layer) and the functional layer (B layer), the film forming conditions such as the heat fixation temperature were changed as shown in Table 7, and a biaxially stretched film was obtained by the same method as in Comparative Example 1. rice field. Next, the composite oxide thin film layer of silicon dioxide and aluminum oxide was formed on the corona-treated surface of the obtained biaxially stretched polyamide film. In Comparative Example 4-3, the inorganic thin film layer was not formed.
  • Table 7 shows the physical characteristics and various evaluation results of the biaxially stretched polyamide film produced in Comparative Example 4.
  • the biaxially stretched polyamide film containing no material for modifying the bending pinhole resistance of Comparative Example 4-1 was inferior in bending pinhole resistance.
  • the bending pinhole resistance of the film was inferior because the amount of the material for modifying the bending pinhole resistance was too small.
  • Comparative Example 4-3 since the inorganic thin film layer was not formed, the oxygen permeability was large and it was not suitable as a gas barrier film.
  • Comparative Example 4-4 since there were too many materials for modifying the bending pinhole resistance, the bending pinhole resistance was excellent, but the impact strength, piercing strength, and friction pinhole resistance of the film were inferior.
  • the functional layer to be the surface layer contained a material for modifying the bending pinhole resistance, so that the friction pinhole resistance was inferior. In addition, deteriorated substances adhered to the lip of the die in the extrusion process.
  • the conventionally used polyamide elastomer and polyester elastomer were used as materials for modifying the bending pinhole resistance, so that although the bending pinhole resistance was excellent, the impact strength and puncture resistance of the film were pierced. The strength and abrasion resistance were inferior.
  • the biaxially stretched polyamide film of the present invention is excellent in impact resistance, bending pinhole resistance and friction pinhole resistance at the same time, it can be suitably used for applications of packaging materials such as food packaging. Furthermore, since the elastomer component does not deteriorate inside the die, it is possible to suppress the adhesion of deteriorated substances to the inner surface of the die and the adhesion of rheumatism to the outlet of the die slip for a long time, stop production and clean the lip of the die. It is possible to reduce the frequency of the operation and enable continuous production for a long time.

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WO2023176213A1 (ja) * 2022-03-16 2023-09-21 東洋紡株式会社 二軸配向ポリアミドフィルム
JP2023151064A (ja) * 2022-03-31 2023-10-16 東洋紡株式会社 易裂性二軸延伸ポリアミドフィルム
JP7452744B1 (ja) 2023-06-19 2024-03-19 Ｔｏｐｐａｎホールディングス株式会社 積層体、包装袋及び包装体
JP2024051845A (ja) * 2022-09-30 2024-04-11 東洋紡株式会社 包装用積層フィルム
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WO2024157875A1 (ja) * 2023-01-23 2024-08-02 東洋紡株式会社 二軸延伸ポリアミドフィルム、および包装材料
EP4494847A4 (en) * 2022-03-16 2026-03-18 Toyo Boseki BIAXIALLY ORIENTED POLYAMIDE FILM

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