Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a laminate, a film, a method for producing a film, and a film for forming an inorganic vapor deposition film, etc.
• biodegradable plastics include polybutylene succinate (hereinafter abbreviated as PBS), polybutylene terephthalate/adipate (hereinafter abbreviated as PBAT), polybutylene succinate/terephthalate (hereinafter abbreviated as PBST), and polylactic acid (hereinafter abbreviated as PLA).
• PBS polybutylene succinate
• PBAT polybutylene terephthalate/adipate
• PBST polybutylene succinate/terephthalate
• PLA polylactic acid
• PBSA polybutylene succinate/adipate
• PHA polyhydroxyalkanoate
• resins that have a certain degree of biodegradability, especially in the ocean.
• PHAs include poly(3-hydroxybutyrate) (hereinafter abbreviated as PHB), poly(3-hydroxybutyrate/3-hydroxyvalerate) (hereinafter abbreviated as PHBV), poly(3-hydroxybutyrate/3-hydroxyhexanoate) (hereinafter abbreviated as PHBH), and poly(3-hydroxybutyrate/4-hydroxybutyrate).
• PHB poly(3-hydroxybutyrate)
• PHBV poly(3-hydroxybutyrate/3-hydroxyvalerate)
• PHBH poly(3-hydroxybutyrate/3-hydroxyhexanoate)
• PHBH poly(3-hydroxybutyrate/4-hydroxybutyrate
• Patent Document 1 discloses a vapor-deposited biodegradable film in which a transparent vapor-deposited layer of metal oxide is formed on one side of a plastic film whose main component is a biodegradable resin made of an aliphatic diol and an aliphatic dicarboxylic acid, and shows a film that is flexible, completely biodegradable, and has high barrier properties.
• Patent Document 2 discloses a molded body including a laminate in which a vapor deposition layer containing an inorganic material is provided on at least one side of a resin layer using a poly(3-hydroxybutyrate) resin, and shows that forming a vapor deposition layer on a surface of a resin layer having a surface tension of 36 mN/m or more improves the adhesion and gas barrier properties of the vapor deposition layer.
• Patent Document 3 discloses a film in which an inorganic vapor deposition film is formed on a resin layer whose main component is a biodegradable resin made of a specific aliphatic diol and an aliphatic dicarboxylic acid, as well as a laminate or packaging material in which the film is bonded to a substrate, and shows that it is possible to achieve both soil and marine degradability and barrier properties.
• a resin shows not only room temperature biodegradability but also marine biodegradability (marine biodegradability), then for example, a film made of biodegradable resin can be treated as a home compost after use, and furthermore, by biodegrading in the ocean, it is possible to eliminate the adverse impact of microplastics on marine life.
• Patent Document 1 allows biodegradation under conditions that are relatively favorable for biodegradation, but biodegradability in aerobic compost at room temperature, in soil environments, and in the sea cannot be said to be sufficient.
• Patent Documents 2 and 3 are deposited on resin films that are biodegradable in aerobic compost at room temperature, in soil environments, and in the sea, and thus degradability can be guaranteed, but the adhesion of the inorganic vapor-deposited film is not satisfactory.
• the present invention has been made in consideration of the problems inherent in the above-mentioned conventional technologies, and aims to provide a laminate or film that has excellent adhesion between a resin layer and an inorganic vapor deposition film, as well as excellent biodegradability, particularly excellent biodegradability at room temperature and excellent marine biodegradability.
• Another object of the present invention is to provide a method for producing a film that has excellent adhesion between a resin layer and an inorganic vapor deposition film, as well as excellent biodegradability.
• Still another object of the present invention is to provide a film for forming an inorganic vapor deposition film that has excellent adhesion to an inorganic vapor deposition film and exhibits excellent biodegradability.
• Still another object of the present invention is to provide a new use for a specific resin that has excellent biodegradability.
• the gist of the present invention lies in the following [1] to [56].
• the resin layer contains a first aliphatic polyester-based resin (A),
• the first aliphatic polyester resin (A) contains, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid,
• the repeating structural unit A2 derived from an aliphatic dicarboxylic acid includes at least a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• the repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content (A11/A1) of the repeating structural unit A11 relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester-based resin (A) is 95 mol % or more and 100 mol % or less; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22/A2) is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21/A2) is 50 mol % or more and 89 mol % or less,
• the laminate according to any one of [1] to [9], wherein a content (A23/A2) of the repeating structural unit A23 derived from adipic acid relative to the number of moles of the repeating structural unit A2 is 0 mol %
• the repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 relative to the number of moles of the repeating structural unit A1 (A11/A1) is 95 mol % or more and 100 mol % or less; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22/A2) is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21/A2) is 50 mol % or more and 89 mol % or less,
• the laminate according to any one of [1] to [9], wherein the content of the repeating structural unit A23 derived from adipic acid relative to the number of moles of the repeating structural unit A2 (A23/A2) is equal to or greater than 0 mol % and less than 11 mol %.
• the resin layer further contains at least one selected from the group consisting of a second aliphatic polyester resin (B1), an aliphatic-aromatic polyester resin (B2), a third aliphatic polyester resin (B3), and a polyhydroxyalkanoate (C);
• the second aliphatic polyester resin (B1) is at least one resin selected from the group consisting of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA)
• the aliphatic aromatic polyester resin (B2) is at least one resin selected from the group consisting of polybutylene succinate terephthalate (PBST) and polybutylene adipate terephthalate (PBAT)
• the third aliphatic polyester-based resin (B3) is at least one resin selected from the group consisting of polylactic acid (PLA) and polycaprolactone (PCL),
• the laminate according to any one of [1] to [13], wherein the polyhydroxyalkanoate (C) is a resin different from
• the repeating structural unit A2 includes at least a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms. film.
• the repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content (A11/A1) of the repeating structural unit A11 relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester-based resin (A) is 95 mol % or more and 100 mol % or less; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22/A2) is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21/A2) is 50 mol % or more and 89 mol % or less,
• the film according to any one of [27] to [34], wherein a content (A23/A2) of the repeating structural unit A23 derived from adipic acid relative to the number of moles of the repeating structural unit A2 is 0 mol %
• the repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 relative to the number of moles of the repeating structural unit A1 (A11/A1) is 95 mol % or more and 100 mol % or less; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22/A2) is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21/A2) is 50 mol % or more and 89 mol % or less,
• the film according to any one of [27] to [34], wherein the content of the repeating structural unit A23 derived from adipic acid relative to the number of moles of the repeating structural unit A2 (A23/A2) is 0 mol % or more and less than 11 mol %.
• the resin layer further contains at least one selected from the group consisting of a second aliphatic polyester resin (B1), an aliphatic aromatic polyester resin (B2), a third aliphatic polyester resin (B3), and a polyhydroxyalkanoate (C);
• the second aliphatic polyester resin (B1) is at least one resin selected from the group consisting of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA)
• the aliphatic aromatic polyester resin (B2) is at least one resin selected from the group consisting of polybutylene succinate terephthalate (PBST) and polybutylene adipate terephthalate (PBAT)
• the third aliphatic polyester-based resin (B3) is at least one resin selected from the group consisting of polylactic acid (PLA) and polycaprolactone (PCL),
• the film according to any one of [27] to [39], wherein the polyhydroxyalkanoate (C) is a resin different from the first
• the vapor-deposited film contains, as a main component, at least one selected from the group consisting of aluminum, an aluminum alloy, silicon oxide, aluminum oxide, and a complex of silicon oxide and aluminum oxide.
• a method for producing a film having a resin layer and an inorganic vapor deposition film provided on at least one surface of the resin layer comprising: a film forming step of forming an inorganic vapor deposition film on at least one surface of the resin layer, the resin layer comprises a first aliphatic polyester-based resin (A) including, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid, the repeating structural units A1 and A2 including at least a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms; A method for manufacturing a film.
• a first aliphatic polyester-based resin including, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic
• a film for forming an inorganic vapor-deposited film comprising a first aliphatic polyester-based resin (A),
• the first aliphatic polyester resin (A) contains, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid,
• the repeating structural unit A2 includes at least a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms
• the film for forming an inorganic vapor deposition film has a bio-based carbon content of 25% or more and a crystallization half time at a temperature of 50° C.
• a film having a resin layer and an inorganic vapor-deposited film provided on at least one surface of the resin layer for improving biodegradability comprising: Use of a first aliphatic polyester-based resin (A), wherein the first aliphatic polyester-based resin (A) has a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid, and the repeating structural unit A2 includes, as main structural units, a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• a first aliphatic polyester-based resin (A) in a resin layer to improve biodegradability of a laminate having a base layer, a vapor-deposited film, and a resin layer laminated in this order, the first aliphatic polyester-based resin (A) having a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid, the repeating structural unit A2 including a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• the present invention it is possible to provide a laminate and a film that have excellent adhesion between the resin layer and the inorganic vapor deposition film, and that have excellent biodegradability of the resin layer, particularly excellent biodegradability at room temperature and excellent marine biodegradability. Furthermore, according to the present invention, it is possible to provide a method for producing a film that has excellent adhesion between the resin layer and the inorganic vapor deposition film, and that has excellent biodegradability of the resin layer. Furthermore, according to the present invention, it is possible to provide a film for forming an inorganic vapor deposition film that has excellent adhesion to the inorganic vapor deposition film and exhibits excellent biodegradability. Furthermore, according to the present invention, it is possible to provide a new use for a specific resin that has excellent biodegradability.
• the expression "A or B” can be read as "at least one selected from the group consisting of A and B.”
• a description such as “at least one selected from the group consisting of XX, YY, and ZZ” means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.
• mass % and “weight %” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
• a laminate or film that contributes to achieving the above-mentioned object can be obtained by incorporating in the resin layer a first aliphatic polyester-based resin (A) that contains, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid, and that contains, as the repeating structural unit A2 derived from the aliphatic dicarboxylic acid, a repeating structural unit derived from a specific aliphatic dicarboxylic acid, in a laminate having a base layer, a vapor-deposited film, and a resin layer in this order, or a film having a resin layer and a vapor-deposited film provided on at least one surface of the resin layer, and have thus completed the present invention.
• A first aliphatic polyester-based resin
• a laminate according to one embodiment of the present invention has a base layer, a vapor-deposited film, and a resin layer in this order,
• the resin layer contains a first aliphatic polyester-based resin (A)
• the first aliphatic polyester resin (A) contains, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid
• the repeating structural unit A2 derived from an aliphatic dicarboxylic acid includes at least a repeating structural unit A21 derived from succinic acid, and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• a film having a laminated structure according to one embodiment of the present invention (hereinafter, may be simply referred to as a "film” or a “laminate film”) has a resin layer and a vapor-deposited film provided on at least one surface of the resin layer,
• the resin layer comprises a first aliphatic polyester-based resin (A), which comprises, as main structural units, a repeating structural unit A1 derived from an aliphatic diol and a repeating structural unit A2 derived from an aliphatic dicarboxylic acid, and the repeating structural unit A2 comprises at least a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• A first aliphatic polyester-based resin
• the above laminates and films exhibit excellent biodegradability because the resin layer contains a first aliphatic polyester-based resin (A) (hereinafter also referred to simply as “aliphatic polyester-based resin (A)” or “polyester-based resin (A)”) which has excellent biodegradability at room temperature (home compostability) and marine biodegradability.
• the resin layer has a high surface wetting tension, i.e., a high surface tension.
• the resin layer has a low surface roughness, for example, the arithmetic mean height (arithmetic mean roughness) Ra of a roughness curve based on Japanese Industrial Standards (JIS) B0601:2001. That is, the surface smoothness is high.
• the resin layer has excellent adhesion to a vapor deposition film.
• the present inventors speculate as follows about the reason why the resin layer containing the aliphatic polyester resin (A) has a higher surface wetting tension and a lower surface roughness than the resin layers containing other biodegradable resins.
• the repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms contained in the aliphatic polyester resin (A) has a longer main chain than the repeating structural unit derived from an aliphatic dicarboxylic acid in the aliphatic polyester resin used in conventional laminates and films in which an inorganic vapor deposition film is applied to a resin layer.
• the aliphatic polyester resin (A) has a relatively low crystallinity, and as a result, it is considered that the surface roughness of the resin layer is reduced and the surface is smooth.
• the relatively low crystallinity of the aliphatic polyester resin (A) makes it difficult for low molecular weight components to bleed out to the surface of the resin layer. As a result, it is considered that the surface tension of the resin layer is increased.
• a polyester film containing an aliphatic polyester-based resin (A) capable of constituting the resin layer has at least one surface that has a wetting tension and/or surface roughness suitable for forming an inorganic vapor deposition film on that surface, and can become a polyester film for forming an inorganic vapor deposition film (hereinafter also simply referred to as a "film for forming an inorganic vapor deposition film") that is particularly suitable for forming an inorganic vapor deposition film on that surface.
• this specification discloses that all matters relating to the resin layer disclosed hereinafter can be applied to all of the laminates, films (laminate films), and films for forming inorganic vapor deposition films according to the present invention described above, unless otherwise specified.
• an aliphatic diol refers to a compound in which two hydroxyl groups are bonded to an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group is usually a straight-chain aliphatic hydrocarbon group, but may have a branched structure or a cyclic structure, or may have a plurality of these structures.
• an aliphatic dicarboxylic acid refers to a compound in which two carboxyl groups are bonded to an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group is usually a straight-chain aliphatic hydrocarbon group, but may have a branched structure, may have a cyclic structure, or may have a plurality of these structures.
• the aliphatic polyester resin (A) is a polymer having repeating units, and each repeating unit is also called a compound unit corresponding to the compound from which the repeating unit is derived.
• a repeating unit derived from an aliphatic diol is also called an "aliphatic diol unit”
• a repeating unit derived from an aliphatic dicarboxylic acid is also called an "aliphatic dicarboxylic acid unit.”
• the repeating structural unit A1 derived from an aliphatic diol means a repeating structural unit corresponding to an aliphatic diol, that is, a repeating structural unit formed by the reaction of two hydroxyl groups possessed by an aliphatic diol.
• the repeating structural unit A2 derived from an aliphatic dicarboxylic acid means a repeating structural unit corresponding to an aliphatic dicarboxylic acid, that is, a repeating structural unit formed by the reaction of two carboxy groups possessed by an aliphatic dicarboxylic acid.
• the "repeating structural unit A21 derived from succinic acid” means a "structural unit corresponding to succinic acid", that is, a structural unit formed by the reaction of two carboxy groups possessed by succinic acid.
• the "repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms” means a "structural unit corresponding to an aliphatic dicarboxylic acid having 9 to 36 carbon atoms", that is, a structural unit formed by the reaction of two carboxy groups possessed by an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• the "main structural unit” in the aliphatic polyester resin (A) usually means a structural unit that is contained in the aliphatic polyester resin (A) at 80 mol% or more, and when no structural unit other than the main structural unit is contained, that is, the structural unit may be 100 mol%.
• having the aliphatic diol unit A1 and the aliphatic dicarboxylic acid unit A2 as the main structural units means that the sum of the moles of the aliphatic diol unit A1 and the aliphatic dicarboxylic acid unit A2 is 80 mol% or more and 100 mol% or less with respect to the total moles of the structural units of the aliphatic polyester resin (A).
• the moles of the repeating structural units in the aliphatic polyester resin (A) are counted as 1 mole of the smallest ester unit of the aliphatic polyester resin (A).
• the "main structural unit” in other resins for example, the “main structural unit” in the polyhydroxyalkanoate (C) described later, the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), and the third aliphatic polyester resin (B3).
• the resin layer according to the present invention can be formed from a resin composition containing an aliphatic polyester resin (A).
• a resin composition containing an aliphatic polyester resin (A).
• the aliphatic polyester resin (A) contains, as main constituent units, an aliphatic diol unit A1 and an aliphatic dicarboxylic acid unit A2.
• the aliphatic dicarboxylic acid unit A2 includes at least a succinic acid unit A21 and an aliphatic dicarboxylic acid unit A22 having a carbon number of 9 to 36.
• the aliphatic diol unit A1 is not particularly limited, but from the viewpoint of the mechanical strength and moldability of the resin layer containing the aliphatic polyester resin (A) and from the viewpoint of easier adjustment, it is preferable that the aliphatic diol unit A11 contains a repeating structural unit A11 derived from an aliphatic diol having 2 to 10 carbon atoms, and the aliphatic diol unit A11 is particularly preferably an aliphatic diol unit having 4 to 6 carbon atoms.
• aliphatic diol unit A11 examples include, for example, an ethylene glycol unit, a 1,3-propanediol unit, a 1,4-butanediol unit, and a 1,4-cyclohexanedimethanol unit.
• the aliphatic diol unit A11 is a repeating structural unit A11 derived from 1,4-butanediol, that is, a 1,4-butanediol unit A11.
• the resin composition (resin layer) may contain one type of aliphatic polyester resin (A) alone or two or more types of aliphatic polyester resin (A).
• the content of aliphatic dicarboxylic acid units A2 in the aliphatic polyester resin (A) is not particularly limited, and from the viewpoint of biodegradability, it is usually 25 mol% or more, preferably 30 mol% or more, more preferably 35 mol% or more, even more preferably 40 mol% or more, and particularly preferably 45 mol% or more, relative to 100 mol% of all constituent units constituting the aliphatic polyester resin (A), and is usually 75 mol% or less, preferably 70 mol% or less, more preferably 65 mol% or less, even more preferably 60 mol% or less, and particularly preferably 55 mol% or less.
• the content of the aliphatic diol unit A1 in the aliphatic polyester resin (A) is not particularly limited, and from the viewpoint of biodegradability, it is usually 25 mol% or more, preferably 30 mol% or more, more preferably 35 mol% or more, even more preferably 40 mol% or more, and particularly preferably 45 mol% or more, relative to 100 mol% of all constituent units constituting the aliphatic polyester resin (A), and is usually 75 mol% or less, preferably 70 mol% or less, more preferably 65 mol% or less, even more preferably 60 mol% or less, and particularly preferably 55 mol% or less.
• the content of succinic acid units A21 in the aliphatic polyester resin (A) is not particularly limited, but from the viewpoint of moldability, the content of succinic acid units A21 in the aliphatic dicarboxylic acid units A2 in the aliphatic polyester resin (A) (A21/A2) is preferably 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and is usually 99 mol% or less, preferably 95 mol% or less, and from the viewpoint of biodegradation rate and surface smoothness, it is more preferably 91 mol% or less, and even more preferably 89 mol% or less.
• the content of the succinic acid units A21 (A21/A2) is preferably 50 mol% or more and 99 mol% or less, particularly preferably 50 mol% or more and 95 mol% or less, even more preferably 50 mol% or more and 91 mol% or less, still more preferably 50 mol% or more and 89 mol% or less, particularly preferably 60 mol% or more and 89 mol% or less, and even more preferably 70 mol% or more and 89 mol% or less.
• the content of the aliphatic dicarboxylic acid unit A22 having 9 to 36 carbon atoms in the aliphatic polyester resin (A) is not particularly limited, but from the viewpoint of the surface smoothness of the resin layer, the biodegradation rate, and moldability, the content (A22/A2) of the aliphatic dicarboxylic acid unit A22 having 9 to 36 carbon atoms in the aliphatic dicarboxylic acid unit A2 in the aliphatic polyester resin (A) is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, particularly preferably 9 mol% or more, particularly preferably 10 mol% or more, and even more preferably 11 mol% or more.
• the content (A22/A2) of the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms is preferably 1 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 40 mol% or less, even more preferably 7 mol% or more and 40 mol% or less, particularly preferably 9 mol% or more and 30 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, and further preferably 11 mol% or more and 30 mol% or less.
• the content of the aliphatic diol units A11 having 2 to 10 carbon atoms in the aliphatic polyester resin (A) is not particularly limited, but from the viewpoint of heat resistance, the content of the aliphatic diol units A11 having 2 to 10 carbon atoms (A11/A1) based on the total number of moles of the aliphatic diol units A1 in the aliphatic polyester resin (A) is preferably 90 mol % or more and 100 mol % or less, and particularly preferably 95 mol % or more and 100 mol % or less.
• each dicarboxylic acid unit in all polyester resins contained in the resin composition contains the content of succinic acid units and aliphatic dicarboxylic acid units having 9 to 36 carbon atoms in all polyester resins contained in the resin composition relative to the aliphatic dicarboxylic acid units in all polyester resins contained in the resin composition satisfies the following range.
• the ratio (content) of the total number of moles of succinic acid units contained in the resin composition to the total number of moles of aliphatic dicarboxylic acid units in all polyester resins contained in the resin composition is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, and also preferably 99 mol% or less, more preferably 98 mol% or less, even more preferably 97 mol% or less, and particularly preferably 96 mol% or less.
• the ratio (content) of the total number of moles of aliphatic dicarboxylic acid units having 9 to 36 carbon atoms contained in the resin composition to the total number of moles of aliphatic dicarboxylic acid units in all polyester resins contained in the resin composition is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 3 mol% or more, particularly preferably 4 mol% or more, especially preferably 5 mol% or more, and also preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, and especially preferably 30 mol% or less.
• the content of aliphatic dicarboxylic acid units having 9 to 36 carbon atoms in all polyester resins in the resin composition is preferably 1 mol% or more and 60 mol% or less, particularly preferably 1 mol% or more and 50 mol% or less, even more preferably 2 mol% or more and 50 mol% or less, still more preferably 3 mol% or more and 40 mol% or less, particularly preferably 4 mol% or more and 40 mol% or less, even more preferably 5 mol% or more and 40 mol% or less, and even more preferably 5 mol% or more and 30 mol% or less.
• One embodiment of the aliphatic polyester resin (A) according to the present invention is, for example, an aliphatic polyester resin (A) containing an aliphatic diol unit A1 represented by the following structural formula (1), a succinic acid unit A21 represented by the following structural formula (2), and an aliphatic dicarboxylic acid unit A22 represented by the following structural formula (3).
• the aliphatic polyester resin (A) according to this embodiment may contain two or more types of the aliphatic diol unit A1 represented by the following structural formula (1), may contain two or more types of the aliphatic dicarboxylic acid unit A22 represented by the following structural formula (3), and may further have structural units other than these structural units.
• -O-R 1 -O- (1) -OC-CH 2 -CH 2 -CO- (2) -OC-R 2 -CO- (3)
• the aliphatic diol unit A1, the aliphatic dicarboxylic acid unit A21, and the aliphatic dicarboxylic acid unit A22 represented by the above structural formulas (1), (2), and (3) may be derived from a compound derived from petroleum or a compound derived from a plant raw material, but are preferably derived from a compound derived from a plant raw material. Therefore, the bio-based carbon content of the aliphatic polyester resin (A) according to the present disclosure in accordance with ISO16620-2:2015 is preferably 10% or more, particularly preferably 25% or more. The upper limit is not particularly limited, and may be 100% or less. Therefore, the bio-based carbon content of the aliphatic polyester resin (A) is preferably 10% or more and 100% or less, and more preferably 25% or more and 100% or less.
• the types of the substituents and/or atoms are not particularly limited as long as the effects of the present invention can be obtained, and examples of the substituents and/or atoms that can be independently substituted include a halogen atom, a cyano group, an amino group, an ester group, an alkylcarbonyl group, an acetyl group, a silyl group, a boryl group, a nitrile group, a thio group, a seleno group, etc. These substituents and/or atoms may be of only one type or of two or more types.
• the aliphatic diol that gives the diol unit A1 represented by the structural formula (1) is not particularly limited, but from the viewpoint of moldability and mechanical strength, an aliphatic diol having 2 to 10 carbon atoms is preferred, and an aliphatic diol having 4 to 6 carbon atoms is particularly preferred.
• Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol, and among these, 1,4-butanediol is particularly preferred. It is also possible to use two or more types of the aliphatic diols.
• the aliphatic dicarboxylic acid that gives the aliphatic dicarboxylic acid unit A22 represented by the structural formula (3) is not particularly limited as long as it is an aliphatic dicarboxylic acid having 9 to 36 carbon atoms, but from the viewpoint of heat resistance, an aliphatic dicarboxylic acid having 9 to 13 carbon atoms is preferred.
• Examples of aliphatic dicarboxylic acids having 9 to 36 carbon atoms include azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, etc., and among these, azelaic acid and sebacic acid are particularly preferred.
• a specific example of the aliphatic polyester-based resin (A) according to the present disclosure includes a resin containing polybutylene succinate sebacate (PBSSe) composed of aliphatic diol units A1, succinic acid units A21 as aliphatic dicarboxylic acid units A2, and sebacic acid units as aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms. More typically, the aliphatic polyester-based resin (A) is PBSSe.
• PBSSe polybutylene succinate sebacate
• the aliphatic polyester resin (A) may have one or more aliphatic dicarboxylic acid units A23 other than the succinic acid units A21 and the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms (hereinafter, these may be referred to as "other aliphatic dicarboxylic acid units") for the purpose of controlling heat resistance or strength and/or controlling biodegradability.
• the total content (A23/A2) of the other aliphatic dicarboxylic acid structural units A23 relative to the aliphatic dicarboxylic acid units A2 in the aliphatic polyester resin (A) is usually 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably less than 11 mol% relative to 100 mol% of all dicarboxylic acid units in the aliphatic polyester resin (A).
• the lower limit is not particularly limited, and is, for example, 0 mol%. That is, based on all the dicarboxylic acid units A2 in the aliphatic polyester resin (A), the content of the other aliphatic dicarboxylic acid units A23 (A23/A2) is preferably 0 mol % or more and 50 mol % or less, particularly preferably 0 mol % or more and 30 mol % or less, more preferably 0 mol % or more and 20 mol % or less, and particularly preferably 0 mol % or more and less than 11 mol %.
• Examples of the aliphatic dicarboxylic acid that provides the other aliphatic dicarboxylic acid unit A23 include at least one aliphatic dicarboxylic acid selected from the group consisting of oxalic acid, malonic acid, and adipic acid.
• aliphatic polyester resin (A) according to this embodiment having the other aliphatic carboxylic acid unit A23 include those in which the repeating structural unit A1 contains 1,4-butanediol units A11, and the content of the 1,4-butanediol units A11 (A11/A1) relative to the total number of moles of the repeating structural units A1 in the aliphatic polyester resin (A) is 95 mol % or more and 100 mol % or less, and
• aliphatic polyester-based resins (A) in which the content of the repeating structural unit A22 (A22/A2) is 11 mol% or more and 30 mol% or less, the content of the repeating structural unit A21 (A21/A2) relative to the total number of moles of the repeating structural unit A2 is 50 mol% or more and 89 mol% or less, and the content of adipic acid units A23 (A23/A2) relative to the total number of moles
• the ratio ((A22/A2)/(A23/A2)) of the content (A22/A2) to the content (A23/A2) is preferably more than 1, particularly preferably 2 or more, from the viewpoints of surface smoothness and biodegradation rate, and the upper limit is not particularly limited.
• the repeating structural unit A1 contains 1,4-butanediol units A11, the content of 1,4-butanediol units A11 (A11/A1) relative to the total number of moles of the repeating structural unit A1 in the aliphatic polyester resin (A) is 95 mol % or more and 100 mol % or less, and the content of the repeating structural unit A11 relative to the total number of moles of the repeating structural unit A2 is 95 mol % or more and 100 mol % or less.
• the content of repeating structural unit A22 is 11 mol% or more and 30 mol% or less
• the content of repeating structural unit A21 (A21/A2) relative to the total number of moles of repeating structural unit A2 is 50 mol% or more and 89 mol% or less
• the content of adipic acid unit A23 (A23/A2) relative to the total number of moles of repeating structural unit A2 is 0 mol% or more and 20 mol% or less
• the ratio ((A22/A2)/(A23/A2)) exceeds 1.
• the aliphatic polyester resin (A) may further have a repeating structural unit (aliphatic oxycarboxylic acid unit) A3 derived from an aliphatic oxycarboxylic acid.
• aliphatic oxycarboxylic acid component that gives the aliphatic oxycarboxylic acid unit A3 include, for example, aliphatic oxycarboxylic acids such as lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, or 2-hydroxyisocaproic acid, or derivatives such as lower alkyl esters or intramolecular esters of these aliphatic oxycarboxylic acids.
• optical isomers When optical isomers exist, they may be any of D-, L-, or racemic forms. Among these, lactic acid or glycolic acid, or derivatives thereof, are particularly preferred. These aliphatic oxycarboxylic acids may be used alone or as a mixture of two or more. The form of the aliphatic oxycarboxylic acid component used as a raw material may be any of solid, liquid, or aqueous solution.
• the content is preferably 20 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, and most preferably 0 mol% (not included, i.e., below the detection limit) when all the constituent units constituting the polyester resin (A) are taken as 100 mol%, from the viewpoint of moldability.
• the content of the aliphatic oxycarboxylic acid units A3 is preferably 0 mol% or more and 20 mol% or less, particularly preferably 0 mol% or more and 10 mol% or less, even more preferably 0 mol% or more and 5 mol% or less, and most preferably 0 mol% (not included, i.e., below the detection limit), based on the number of moles of all the constituent units of the aliphatic polyester resin (A) (100 mol%).
• the aliphatic polyester resin (A) may also contain aromatic dicarboxylic acid units such as furandicarboxylic acid, terephthalic acid, or isophthalic acid as dicarboxylic acid units other than the aliphatic dicarboxylic acid units, to the extent that the effects of the present invention are not impaired.
• aromatic dicarboxylic acid units such as furandicarboxylic acid, terephthalic acid, or isophthalic acid as dicarboxylic acid units other than the aliphatic dicarboxylic acid units, to the extent that the effects of the present invention are not impaired.
• the melt viscosity of the aliphatic polyester resin (A) may be increased by copolymerizing an aliphatic polyhydric alcohol having three or more functionalities, an aliphatic polycarboxylic acid having three or more functionalities or an acid anhydride thereof, or an aliphatic polyoxycarboxylic acid having three or more functionalities.
• trifunctional aliphatic polyhydric alcohols include trimethylolpropane, glycerin, etc.
• specific examples of tetrafunctional aliphatic polyhydric alcohols include pentaerythritol, etc. These may be used alone or in combination of two or more.
• Specific examples of trifunctional aliphatic polycarboxylic acids or their anhydrides include propane tricarboxylic acid or its anhydride, etc.
• tetrafunctional polycarboxylic acids or their anhydrides include cyclopentane tetracarboxylic acid or its anhydride, etc. These may be used alone or in combination of two or more.
• Trifunctional aliphatic oxycarboxylic acid components are divided into (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, and (ii) a type having one carboxyl group and two hydroxyl groups in the same molecule. Either type can be used, but from the viewpoint of moldability, mechanical strength, and the appearance of the molded product, (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, such as malic acid, is preferred, and more specifically, malic acid is preferably used.
• tetrafunctional aliphatic oxycarboxylic acid components are divided into (i) a type sharing three carboxyl groups and one hydroxyl group in the same molecule, (ii) a type sharing two carboxyl groups and two hydroxyl groups in the same molecule, and (iii) a type sharing three hydroxyl groups and one carboxyl group in the same molecule.
• Either type can be used, but those having multiple carboxyl groups are preferred, and more specifically, citric acid, tartaric acid, etc. can be mentioned. These may be used alone or in combination of two or more.
• the content thereof, with all structural units constituting the polyester resin (A) taken as 100 mol %, is generally 0 mol % or more in lower limit, preferably 0.01 mol % or more in upper limit, and generally 5 mol % or less, preferably 2.5 mol % or less in upper limit.
• the molecular weight of the aliphatic polyester resin (A) can be measured by gel permeation chromatography (GPC).
• the weight average molecular weight (Mw) of the aliphatic polyester resin (A) using monodisperse polystyrene as the standard is usually 10,000 or more and 1,000,000 or less, but is preferably 20,000 or more and 500,000 or less, more preferably 50,000 or more and 400,000 or less, and even more preferably 100,000 or more and 300,000 or less, because this is advantageous in terms of moldability and mechanical strength.
• the melt flow rate (MFR) of the aliphatic polyester resin (A) is a value measured at a temperature of 190° C. and a load of 2.16 kgf according to JIS K7210-1:2014, and is usually 0.1 g/10 min to 100 g/10 min, but from the viewpoints of moldability and mechanical strength, it is preferably 40 g/10 min or less, more preferably 20 g/10 min or less, preferably 1.0 g/10 min or more, and more preferably 2.0 g/10 min or more.
• the MFR of the aliphatic polyester resin (A) can be adjusted by the molecular weight.
• the MFR measured based on JIS K7210-1:2014 at a temperature of 190°C and a load of 2.16 kg is preferably 0.1 g/10 min or more and 100 g/10 min or less, particularly preferably 1.0 g/10 min or more and 40 g/10 min or less, and further preferably 2.0 g/10 min or more and 20 g/10 min or less.
• the melting point of the aliphatic polyester resin (A) is preferably 50° C. or higher, more preferably 70° C. or higher, particularly preferably 80° C. or higher, and also preferably 160° C. or lower, more preferably 140° C. or lower, particularly preferably 120° C. or lower. That is, the melting point of the aliphatic polyester resin (A) is preferably 80° C. or higher and 180° C. or lower, particularly preferably 100° C. or higher and 160° C. or lower, and even more preferably 100° C. or higher and lower than 140° C. In addition, when there are multiple melting points, it is preferable that at least one of the melting points is within the above range.
• the melting point of the aliphatic polyester resin (A) can be measured using a differential scanning calorimeter (e.g., DSC8500 (PerkinElmer Japan)). Specifically, about 5 mg of the aliphatic polyester resin (A) is precisely weighed out, heated and melted under a nitrogen gas flow at a flow rate of 40 mL/min, cooled to room temperature (25°C) at a rate of 10°C/min, and then heated at a rate of 10°C/min to measure the melting point (peak top).
• a differential scanning calorimeter e.g., DSC8500 (PerkinElmer Japan
• the method for producing the aliphatic polyester resin (A) according to the present embodiment can adopt a known method for producing polyester.
• the polycondensation reaction at this time can set appropriate conditions that have been used in the past, and is not particularly limited.
• a method is adopted in which the polymerization degree is further increased by carrying out a decompression operation after the esterification reaction has progressed.
• diol component that forms diol units also referred to as "diol component that provides diol units”
• dicarboxylic acid component that forms dicarboxylic acid units also referred to as “dicarboxylic acid that provides dicarboxylic acid units”
• the diol component and the dicarboxylic acid component react in substantially equimolar amounts, but since the diol component is distilled off during the esterification reaction, it is usually used in a 1 to 50 mol % excess over the dicarboxylic acid component.
• the aliphatic polyester resin (A) contains components (optional components) other than the essential components such as multifunctional component units, the corresponding compounds (monomers and oligomers) are reacted so that the multifunctional component units also have the desired composition.
• the timing or method of introducing the optional components into the reaction system and they can be any as long as they can produce an aliphatic polyester resin (A) suitable for the present invention.
• the aliphatic polyester resin (A) is usually produced in the presence of a catalyst.
• a catalyst Any catalyst that can be used in the production of known polyester resins can be selected as the catalyst, so long as it does not significantly impair the effects of the present invention.
• metal compounds such as germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, or zinc are suitable. Among these, titanium compounds or germanium compounds are suitable.
• Titanium compounds that can be used as catalysts include, for example, organic titanium compounds such as tetraalkoxytitanium compounds such as tetrapropyl titanate, tetrabutyl titanate, and tetraphenyl titanate. Among these, tetrapropyl titanate and tetrabutyl titanate are preferred in terms of price and availability.
• catalysts may be used in combination. Note that one catalyst may be used alone, or two or more catalysts may be used in any combination and ratio.
• the amount of catalyst used is arbitrary as long as it does not significantly impair the effects of the present invention, but is usually 0.0005% by mass or more, more preferably 0.001% by mass or more, and usually 3% by mass or less, preferably 1.5% by mass or less, based on the amount of monomer used.
• the amount of catalyst used is preferably 0.0005% by mass or more and 3% by mass or less, and particularly preferably 0.001% by mass or more and 1.5% by mass or less.
• the timing of introducing the catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be introduced when the raw materials are charged or when pressure reduction begins.
• the reaction conditions such as temperature, polymerization time, and pressure when producing the aliphatic polyester resin (A) can be any as long as they do not significantly impair the effects of the present invention.
• the reaction temperature of the esterification reaction and/or transesterification reaction between the dicarboxylic acid component and the diol component has a lower limit of usually 150°C or more, preferably 180°C or more, and an upper limit of usually 260°C or less, preferably 250°C or less.
• the reaction temperature is preferably 150°C or more and 260°C or less, and particularly preferably 180°C or more and 250°C or less.
• the reaction atmosphere is usually an inert atmosphere such as nitrogen or argon. Furthermore, the reaction pressure is usually normal pressure to 10 kPa, with normal pressure being preferred.
• the lower limit of the reaction time is usually 1 hour or more, and the upper limit is usually 10 hours or less, preferably 6 hours or less, and more preferably 4 hours or less. In other words, the reaction time is preferably 1 hour or more and 10 hours or less, particularly preferably 1 hour or more and 6 hours or less, and more preferably 1 hour or more and 4 hours or less.
• the polycondensation reaction after the esterification reaction and/or transesterification reaction between the dicarboxylic acid component and the diol component is desirably carried out under a vacuum with a lower limit of usually 0.01 ⁇ 10 3 Pa or more, preferably 0.03 ⁇ 10 3 Pa or more, and an upper limit of usually 1.4 ⁇ 10 3 Pa or less, preferably 0.4 ⁇ 10 3 Pa or less. That is, the pressure condition in the polycondensation reaction step is preferably 0.01 ⁇ 10 3 Pa or more and 1.4 ⁇ 10 3 Pa or less, and particularly preferably 0.03 ⁇ 10 3 Pa or more and 0.4 ⁇ 10 3 Pa or less.
• the reaction temperature in the reaction has a lower limit of usually 150° C. or more, preferably 180° C.
• the reaction temperature in the reaction is preferably 150° C. or more and 260° C. or less, and particularly preferably 180° C. or more and 250° C. or less.
• the reaction time has a lower limit of usually 2 hours or more and an upper limit of usually 15 hours or less, preferably 10 hours or less.
• the reaction time is preferably 2 hours or more and 15 hours or less, and particularly preferably 2 hours or more and 10 hours or less.
• the resin layer according to the present invention can be formed from a resin composition containing an aliphatic polyester resin (A).
• the content of the aliphatic polyester resin (A) in the resin composition (resin layer) is not particularly limited, but from the viewpoint of biodegradability, it is usually 5% by mass or more, and preferably 10% by mass or more. %, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more. There is no particular upper limit, and it is usually 100% by mass or less, and 100% by mass or less is more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more.
• the content of the aliphatic polyester resin (A) in the resin composition (resin layer) may be 5 mass % or more and 100 mass % or less based on the mass of the resin composition or the resin layer. % by mass or less, particularly preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 100% by mass or less, particularly preferably 20% by mass or more and 100% by mass or less, and further preferably 25% by mass or more and 100% by mass or less. It is preferably less than mass %.
• the resin composition or the resin layer may contain two or more kinds of aliphatic polyester resins (A). Specifically, for example, the types of constituent units, the ratio of constituent units, the production method, or physical properties may be different.
• the resin composition or the resin layer may contain two or more different aliphatic polyester resins (A).
• the content of the aliphatic polyester resin (A) in the resin composition or the resin layer is the content of all the aliphatic polyester resins (A) in the resin composition or the resin layer.
• the resin composition or the resin layer may further contain a polyhydroxyalkanoate (C) different from the aliphatic polyester resin (A) from the viewpoint of adjusting the rigidity, heat resistance, and biodegradability.
• the polyhydroxyalkanoate (hereinafter sometimes referred to as "PHA") (C) is an aliphatic polyester containing a repeating unit represented by the following structural formula (4). [-CHR-CH 2 -CO-O-] (4) (In structural formula (4), R is an alkyl group having 1 to 15 carbon atoms.)
• polyhydroxyalkanoate (C) may be homopolymers of one type of hydroxyalkanoate, or copolymers composed of two or more types of hydroxyalkanoates or one or more types of hydroxyalkanoates and other monomers.
• homopolymers include poly(3-hydroxybutyrate).
• copolymers examples include poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resins, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resins, poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) copolymer resins, poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resins, and the like.
• the polyhydroxyalkanoate (C) preferably contains, as a structural unit, the structural unit C11 derived from 3-hydroxybutyrate, and from the viewpoint of the balance between the melting point and the decomposition onset temperature, it is more preferable that the polyhydroxyalkanoate (C) further contains at least one structural unit selected from the group consisting of repeating structural units derived from 3-hydroxyvalerate, repeating structural units derived from 3-hydroxyhexanoate, and repeating structural units derived from 4-hydroxybutyrate.
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin ie, PHBH, is preferred.
• polyhydroxyalkanoate (C) has a structural unit C11 derived from 3-hydroxybutyrate, i.e., 3-hydroxybutyrate unit C11, from the viewpoint of moldability and thermal stability, it is preferable that the polyhydroxyalkanoate (C) contains 60 mol% or more of 3-hydroxybutyrate unit C11 relative to 100 mol% of all structural units constituting the polyhydroxyalkanoate (C), particularly preferably 70 mol% or more, and even more preferably 75 mol% or more.
• the upper limit is not particularly limited, but is 100 mol% or less, preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less.
• the content of 3-hydroxybutyrate unit C11 relative to all structural units of polyhydroxyalkanoate (C) is preferably 60 mol% or more and 100 mol% or less, particularly preferably 70 mol% or more and 99 mol% or less, more preferably 75 mol% or more and 97 mol% or less, and especially preferably 75 mol% or more and 95 mol% or less.
• the content is within the above range, crystallization is further promoted, and molding productivity is further improved.
• molding processing becomes easier because the molding temperature and the thermal decomposition temperature can be prevented from becoming close to each other.
• the ratio of each monomer in the polyhydroxyalkanoate (C) can be measured by gas chromatography as follows. To approximately 20 mg of dried PHA, 2 ml of a sulfuric acid/methanol mixture (15/85 (mass ratio)) and 2 ml of chloroform are added, the container is sealed, and heated at 100°C for 140 minutes to obtain the methyl ester of the PHA decomposition product. After cooling, 1.5 g of sodium bicarbonate is gradually added to neutralize the mixture, and the mixture is left to stand until the evolution of carbon dioxide gas stops.
• the monomer unit composition of the PHA decomposition product in the supernatant is analyzed by capillary gas chromatography to determine the ratio of each monomer in the polyhydroxyalkanoate (C).
• the weight average molecular weight (hereinafter sometimes referred to as Mw) of polyhydroxyalkanoate (C) can be measured by the above-mentioned gel permeation chromatography (GPC).
• the weight average molecular weight (Mw) using monodisperse polystyrene as the standard is usually 200,000 or more and 2,500,000 or less, but is preferably 250,000 or more and 2,000,000 or less, and more preferably 300,000 or more and 1,000,000 or less, because this is advantageous in terms of moldability and mechanical strength. Having a weight average molecular weight within the above range can improve the mechanical properties, etc., of the resin layer and moldability.
• the melt flow rate (MFR) of polyhydroxyalkanoate (C) is a value measured at a temperature of 190°C and a load of 2.16 kg according to JIS K7210-1:2014, and is preferably 1 g/10 min or more and 100 g/10 min or less, but from the viewpoint of moldability and mechanical strength, it is more preferably 80 g/10 min or less, and particularly preferably 50 g/10 min or less.
• the MFR of polyhydroxyalkanoate (C) can be adjusted by the molecular weight.
• the above MFR of polyhydroxyalkanoate (C) is preferably 1 g/10 min or more and 100 g/10 min or less, particularly preferably 1 g/10 min or more and 80 g/10 min or less, and more preferably 1 g/10 min or more and 50 g/10 min or less.
• the melting point of polyhydroxyalkanoate (C) is preferably 100°C or higher, more preferably 120°C or higher, and preferably 180°C or lower, more preferably 170°C or lower, and particularly preferably less than 160°C. That is, the melting point of polyhydroxyalkanoate (C) is preferably 100°C or higher and 180°C or lower, particularly preferably 120°C or higher and 170°C or lower, and more preferably 120°C or higher and less than 160°C. When there are multiple melting points, it is preferable that at least one of the melting points is within the above range.
• the polyhydroxyalkanoate (C) is preferably produced by a microorganism.
• examples of such polyhydroxyalkanoates (C) include polyhydroxyalkanoates produced by microorganisms such as Alcaligenes eutrophus AC32 strain (international deposit under the Budapest Treaty, international depositary authority: National Institute of Advanced Industrial Science and Technology Patent Organism Depositary Center (1-1-1 Central 6, Higashi 1-chome, Tsukuba City, Ibaraki Prefecture, Japan), original deposit date: August 12, 1996, transferred on August 7, 1997, deposit number FERM BP-6038 (transferred from original deposit FERM P-15786)) (J. Bacteriol., 179, 4821 (1997)), which is obtained by introducing a PHA synthase gene derived from Aeromonas caviae into Alcaligenes eutrophus.
• polyhydroxyalkanoate (C) examples of commercially available products of the polyhydroxyalkanoate (C) containing 3-hydroxybutyrate units and 3-hydroxyhexanoate units as the main constituent units include "Kaneka Biodegradable Biopolymer Green Planet (registered trademark) X131N,” “Kaneka Biodegradable Biopolymer Green Planet (registered trademark) X131A,” “Kaneka Biodegradable Biopolymer Green Planet (registered trademark) X331N,” and “Kaneka Biodegradable Biopolymer Green Planet (registered trademark) 151C,” all manufactured by Kaneka Corporation.
• One type of polyhydroxyalkanoate (C) may be used, or two or more types of polyhydroxyalkanoates (C) differing in the type of constituent units, the ratio of constituent units, the production method, or physical properties may be blended and used.
• the mass ratio of the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C) contained in the resin composition (resin layer) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total mass of the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C), from the viewpoint of improving rigidity and easiness of molding. Also, it is preferably less than 100% by mass, more preferably 99% by mass or less.
• the content of the aliphatic polyester resin (A) ((A)/((A)+(C)) relative to the total mass of the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C) in the resin layer is preferably 50 mass% or more and less than 100 mass%, particularly preferably 60 mass% or more and less than 100 mass%, further preferably 70 mass% or more and less than 100 mass%, and particularly preferably 80 mass% or more and 99 mass% or less.
• the resin composition may not contain the polyhydroxyalkanoate (C), that is, the content of the aliphatic polyester resin (A) may be 100% by mass.
• the resin composition may contain a resin (other resin) other than the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C) which is an optional component, as long as the effect of the present invention is not impaired.
• the other resin include aromatic polyester resins, polycarbonates, polyamides, polystyrenes, polyolefins, acrylic resins, amorphous polyolefins, ABS, AS (acrylonitrile styrene), polycaprolactone, polyvinyl alcohol, or synthetic resins such as cellulose esters, polylactic acid, aliphatic polyesters such as PBS or PBSA, and biodegradable resins such as aliphatic aromatic polyesters such as PBAT, PBST, or PBSeT.
• the other resins may be used alone or in combination of two or more.
• the resin composition (resin layer) may have, as the other resins, a polyester resin other than the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C) in addition to the aliphatic polyester resin (A) or the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).
• the polyester resins may be, for example, aliphatic polyester resins that do not contain succinic acid units and aliphatic dicarboxylic acid units having 9 to 36 carbon atoms and do not contain the repeating structural unit represented by the structural formula (4), or aliphatic polyester resins that contain only one selected from the group consisting of succinic acid units and aliphatic dicarboxylic acid units having 9 to 36 carbon atoms and do not contain the repeating structural unit represented by the structural formula (4).
• a specific example of such an aliphatic polyester resin is preferably at least one resin selected from the group consisting of a second aliphatic polyester resin (B1) containing an aliphatic diol unit and an aliphatic dicarboxylic acid unit as main structural units, an aliphatic aromatic polyester resin (B2), and a third aliphatic polyester resin (B3) containing an oxycarboxylic acid as main structural unit.
• the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), and the third aliphatic polyester resin (B3) are different from each other, and the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), and the third aliphatic polyester resin (B3) are also different from the first aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).
• Specific examples of the second aliphatic polyester resin (B1) include at least one resin selected from the group consisting of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA).
• aliphatic aromatic polyester resin (B2) include at least one resin selected from the group consisting of polybutylene succinate terephthalate (PBST) and polybutylene adipate terephthalate (PBAT).
• PBST polybutylene succinate terephthalate
• PBAT polybutylene adipate terephthalate
• PCL polycaprolactone
• each dicarboxylic acid unit in all polyester resins contained in the resin composition can be adjusted to satisfy the above-mentioned preferred range by adjusting the amount of succinic acid units or aliphatic dicarboxylic acid units having 9 to 36 carbon atoms in the polyester resins other than the aliphatic polyester resin (A).
• the resin composition (resin layer) contains, in addition to the first aliphatic polyester resin (A), at least one resin selected from the group consisting of the second aliphatic polyester resin (B1), the aliphatic-aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C)
• the mass of the aliphatic polyester resin (A) contained in the resin composition (resin layer) and the mass of the second aliphatic polyester resin (B1), the aliphatic-aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C) are From the viewpoint of improving the rigidity of the molded article of the resin composition and facilitating the molding process
• the content of the aliphatic polyester resin (A) relative to the sum of the aliphatic polyester resin (A) and the total mass of the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C) in the resin layer ((A)/((A)+(B1)+(B2)+(B3)+(C)) is preferably 50% by mass or more and less than 100% by mass, particularly preferably 60% by mass or more and less than 100% by mass, even more preferably 70% by mass or more and less than 100% by mass, and particularly preferably 80% by mass or more and 99% by mass or less.
• the resin composition (resin layer) may not contain the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), the third aliphatic polyester resin (B3) and the polyhydroxyalkanoate (C), i.e., the content of the aliphatic polyester resin (A) may be 100 mass%.
• the resin composition (resin layer) contains at least one resin selected from the group consisting of the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C) in addition to the first aliphatic polyester resin (A), from the viewpoint of more reliably obtaining the effect of the resin composition containing the first aliphatic polyester resin (A), the total polyester resin in the resin composition (resin layer), i.e., the first The content of the second aliphatic polyester resin (B1) relative to the total mass of the first aliphatic polyester resin (A), the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C) [(B1)/((A)+(B1)+(B2)+(B3)+(C))] is preferably 95% by mass or less, more preferably 9
• the lower limit is 0% by mass, while the second aliphatic polyester resin (B1) is both an optional component. Therefore, the content of the second aliphatic polyester resin (B1) in the resin composition (resin layer) is preferably 0 to 95% by mass, particularly preferably 0 to 90% by mass, and more preferably 0 to 55% by mass. From the same viewpoint as above, the total content of the aliphatic aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) relative to the total polyester resin in the resin composition [((B2) + (B3)) / ((A) + (B1) + (B2) + (B3) + (C))] is preferably 50 mass% or less, particularly preferably 40 mass% or less.
• the lower limit is 0 mass%, since the aliphatic aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) are both optional components. Therefore, the total content is preferably 0 to 50 mass%, particularly preferably 0 to 40 mass%. Further, from the same viewpoint as above, the content of polyhydroxyalkanoate (C) relative to the total polyester resin in the resin layer [(C)/((A)+(B1)+(B2)+(B3)+(C))] is preferably 50% by mass or less, particularly preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Moreover, since polyhydroxyalkanoate (C) is an optional component, the lower limit is 0% by mass. That is, the content is preferably 0 to 50% by mass, particularly preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass.
• the resin composition may contain, as "other components", various additives such as inorganic fillers, lubricants, plasticizers, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, hydrolysis inhibitors, crystal nucleating agents, antiblocking agents, light resistance agents, plasticizers, heat stabilizers, flame retardants, release agents, anti-fogging agents, surface wetting improvers, incineration aids, dispersing aids, various surfactants, or slip agents; fine powders of animal/plant substances such as starch, cellulose, paper, wood flour, chitin/chitosan, coconut shell powder, or walnut shell powder; or mixtures thereof.
• additives such as inorganic fillers, lubricants, plasticizers, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, hydrolysis inhibitors, crystal nucleating agents, antiblocking agents, light resistance agents, plasticizers, heat stabilizers, flame retardants, release agents, anti-fogg
• the resin composition may also contain functional additives such as a freshness-preserving agent or an antibacterial agent. These may be blended in any amount within the range that does not impair the effects of the present invention, and one type may be used alone, or two or more types may be mixed and used.
• the content of these other components is usually such that the total amount of the other components is 0.01% by mass or more and 15% by mass or less relative to the total amount of the resin composition so as not to impair the physical properties of the resin composition.
• the content of alkali metal in the resin composition is not particularly limited, but from the viewpoint of biodegradability and long-term storage, it is preferable that it is small. Specifically, it is preferably 50.0 mass ppm or less, more preferably 30.0 mass ppm or less, even more preferably 20.0 mass ppm or less, particularly preferably 10.0 mass ppm or less, particularly preferably 6.0 mass ppm or less, and may be 3.0 mass ppm or less. More preferably, it is preferably 0.0 mass ppm (below detection limit).
• the content can be reduced by purifying the raw material.
• the content of the alkali metal can be measured by a known method such as high-frequency inductively coupled plasma atomic emission spectrometry.
• the resin composition (resin layer) and the film for forming an inorganic vapor deposition film preferably have a bio-based carbon content as defined in ASTM D6866 of 10% or more, particularly preferably 25% or more. There is no particular upper limit, and the bio-based carbon content may be 100% or less. Therefore, the bio-based carbon content of the resin composition (resin layer) and the film for forming an inorganic vapor deposition film is preferably 10% or more and 100% or less, particularly preferably 25% or more and 100% or less. In addition, the resin composition (resin layer) and the inorganic vapor deposition film forming film preferably have a half-crystallization time at a temperature of 50 ° C.
• the half-crystallization time of the resin composition (resin layer) and the inorganic vapor deposition film forming film at a temperature of 50 ° C. is preferably 0.35 minutes or more and 10 minutes or less, particularly preferably 0.38 minutes or more and 8 minutes or less.
• the half-crystallization time can be measured, for example, by the following method. That is, a predetermined amount of a sample taken from the resin composition (resin layer) or the film for forming an inorganic vapor deposition film is placed in an aluminum pan for DSC measurement, and the sample is heated and melted at 200°C for 5 minutes using a differential scanning calorimeter under a nitrogen atmosphere, and then cooled at a rate of 100°C/min. An isothermal crystallization measurement is performed at a temperature of 50°C, and the time required for crystallization to be half-completed at a temperature of 50°C is calculated.
• the resin composition is produced by a method including a mixing step of mixing an aliphatic polyester resin (A), preferably further a polyhydroxyalkanoate (C), other resins used as needed, for example, at least one resin selected from the group consisting of the second aliphatic polyester resin (B1), the aliphatic aromatic polyester resin (B2), and the third aliphatic polyester resin (B3), and other components used as needed.
• A aliphatic polyester resin
• C polyhydroxyalkanoate
• This mixing step is carried out by mixing the aliphatic polyester resin (A), and the polyhydroxyalkanoate (C) that may be further included, other resins, and other components in a predetermined ratio simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder, and preferably melt-kneading them.
• a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder, and preferably melt-kneading them.
• the kneader used in the mixing step may be a melt kneader.
• a twin-screw extruder is more preferable for the purpose of achieving melt kneading depending on the properties of the aliphatic polyester resin (A) used and the polyhydroxyalkanoate (C) that may be contained.
• the temperature during melt kneading is preferably 120 to 220° C., and more preferably 130 to 180° C. Within this temperature range, it is possible to shorten the time required for melt kneading, prevent deterioration of color tone due to deterioration of the resin, and further improve practical physical properties such as impact resistance and moist heat resistance.
• the melt-kneading time should not be unnecessarily long, and is preferably 20 seconds or more and 20 minutes or less, and more preferably 30 seconds or more and 15 minutes or less. It is preferable to set the melt-kneading time so as to satisfy these conditions together with the above temperature.
• the resin layer of the laminate or the laminate film can be obtained by forming the resin composition into a film (film forming).
• Methods for forming a film from a resin composition include, for example, injection molding, extrusion molding, co-extrusion molding (film forming by inflation method or T-die method), lamination molding, heat press molding, blow molding (various types of blow molding), thermoforming (vacuum forming, compressed air forming), plastic processing, powder molding (rotational molding), etc.
• injection molding extrusion molding, co-extrusion molding (film forming by inflation method or T-die method)
• lamination molding heat press molding
• blow molding variable types of blow molding
• thermoforming vacuum forming, compressed air forming
• plastic processing powder molding (rotational molding), etc.
• the method of forming by extrusion molding or inflation molding (inflation method) or the T-die method is particularly preferred because the effects of the present invention are most pronounced.
• a film, sheet or cylindrical material extruded to a predetermined thickness from a T-die, I-die or round die is cooled and solidified using a cooling roll, water, compressed air or the like.
• a cooling roll, water, compressed air or the like it is also possible to form a laminated film by laminating several types of compositions within a range that does not impair the effects of the present invention.
• the conditions such as bubble internal pressure, heating temperature, bubble diameter, cooling rate, and take-up speed can be generally known.
• the blow ratio is usually set to 1.1 to 10 times, preferably 2 to 5 times, so that the tear strength of the film can be adjusted.
• the suitability for inflation molding can be judged by visually observing bubble stability or frost line height, etc. For example, the more stable the bubble is, the more preferable it is, and the more preferable the shape of the bubble is symmetrical. It is preferable that the frost line height is not too high. If the frost line is too high, it indicates that the tubular film is difficult to solidify, and blocking of the film may occur, causing deterioration of the opening. Also, if the frost line is too low, the bubble may come into contact with the air ring or die, making molding impossible. Therefore, the frost line must be at a height suitable for the equipment, raw materials used, and processing conditions.
• the resin temperature inside the die is usually 100°C or higher so that the melt viscosity does not become too high and the extrusion rate per unit power of the extruder is appropriate. On the other hand, it is usually 280°C or lower so that resin deterioration does not adhere to the die and get mixed into the obtained film.
• the resin temperature inside the die is preferably in the range of 110 to 250°C, and more preferably in the range of 120 to 200°C.
• the film obtained by such inflation molding may have a single-layer structure or a laminated structure.
• the thickness of the film produced by inflation molding, that is, the film substrate is usually 6 to 100 ⁇ m, and preferably 10 to 50 ⁇ m.
• the resin temperature inside the die is usually 110°C or higher so that the melt viscosity does not become too high and the extrusion rate per unit power of the extruder is appropriate. On the other hand, it is usually 280°C or lower so that resin deterioration does not adhere to the die and get mixed into the obtained film.
• the resin temperature inside the die is preferably 120 to 250°C, and more preferably 130 to 220°C.
• the surface temperature of the casting roll is usually controlled to 15 to 70°C, preferably 20 to 60°C.
• the sheet thickness is 1 mm or more, it is desirable to use a multi-stage cooling roll.
• Other molding conditions can be normal known conditions.
• the film obtained by T-die molding may also have a single-layer structure or a laminate structure.
• the thickness of the film formed by T-die molding, that is, the film substrate is usually 3 to 200 ⁇ m, and preferably 5 to 100 ⁇ m.
• the film-like molded product obtained by the inflation method or T-die method may then be stretched uniaxially or biaxially by a roll method, tenter method, tubular method, or the like.
• the stretching temperature is usually in the range of 30 to 130°C, and the stretching ratio is in the range of 0.6 to 10 times in the longitudinal and transverse directions, respectively.
• the product may be heat-treated by blowing hot air, irradiating infrared rays, irradiating microwaves, or contacting it with a heat roll, or the like.
• the resin layer and the film for forming an inorganic vapor deposition film preferably have a static friction coefficient of 0.15 to 1.00, more preferably 0.17 to 0.90, measured by the method specified in JIS K7125: 1999.
• the dynamic friction coefficient of the resin layer and the film for forming an inorganic vapor deposition film is preferably 0.15 to 1.00, more preferably 0.17 to 0.90, measured by the method specified in JIS K7125: 1999.
• the arithmetic mean height (arithmetic mean roughness) Ra of the roughness curve of at least one surface (surface on which the inorganic vapor deposition film is formed) of the resin layer and the film for forming an inorganic vapor deposition film, measured by the method specified in JIS B0601:2001, is preferably 0.25 ⁇ m or less, and particularly preferably 0.20 ⁇ m or less.
• the lower limit is not particularly limited, but from the viewpoint of more reliably preventing blocking between the films, it is preferably 0.01 ⁇ m or more, and particularly preferably 0.05 ⁇ m or more.
• the arithmetic mean height Ra is preferably 0.01 ⁇ m or more and 0.25 ⁇ m or less, and particularly preferably 0.05 ⁇ m or more and 0.20 ⁇ m or less.
• a specific method for making the Ra of at least one surface of the resin layer and the film for forming an inorganic vapor deposition film within the above range may be, for example, adjusting the content of aliphatic dicarboxylic acid units having a carbon number of 9 to 36 to a predetermined range.
• the scanning direction of the stylus on the measurement surface of the resin layer and the film for forming an inorganic vapor deposition film may be either MD or TD.
• Ra measured in at least one direction selected from the group consisting of MD and TD is within the above range.
• the reference length and evaluation length of the roughness curve may be determined based on JIS B0633:2001, and for example, the reference length is 0.8 mm and the evaluation length is 4 mm.
• the laminate or film (laminated film) according to the present invention can be obtained by forming an inorganic vapor deposition film on at least one surface of the resin layer or film for forming an inorganic vapor deposition film prepared by the above method (film formation step).
• the method for forming the inorganic vapor deposition film is not particularly limited, and examples thereof include known methods such as EB vapor deposition, induction heating vapor deposition, magnetron sputtering, and CVD.
• the thickness of the inorganic vapor deposition film is preferably 20 nm or more from the viewpoint of imparting sufficient moisture resistance to the laminate or film (laminated film), and is preferably 100 nm or less from an economic viewpoint.
• the thickness of the inorganic vapor deposition film is preferably 20 to 100 nm, and particularly preferably 30 to 70 nm.
• the inorganic substance used as the inorganic vapor deposition film is not particularly limited, and for example, pure aluminum (99.9 mol% or more) can be used.
• a material containing 90.0 to 99.8 mol% aluminum as the main component and 0.2 to 10.0 mol% of at least one additive element selected from the group consisting of magnesium, silicon, tantalum, titanium, boron, calcium, barium, carbon, and manganese is preferable, and a material containing 92 to 99.5 mol% aluminum and 0.5 to 8 mol% additive element is more preferable.
• the transparent deposition material examples include silicon oxide, aluminum oxide, aluminum alloy, a complex of silicon oxide and aluminum oxide, zinc oxide, and titanium oxide. From the viewpoint of ease of handling, it is preferable that the material contains as a main component at least one inorganic substance selected from the group consisting of aluminum, aluminum alloy, silicon oxide, aluminum oxide, and a complex of silicon oxide and aluminum oxide (particularly at least one inorganic substance selected from these), more preferably silicon oxide, aluminum oxide, or silicon oxide-aluminum oxide, and even more preferably silicon oxide or aluminum oxide.
• This oxidation order can be controlled by the oxygen purity of the material during deposition and the amount of oxygen introduced.
• the oxidation order is measured by ESCA. If X is less than 1.0, the film becomes colored and transparency is impaired, which is not preferable. If X exceeds 1.9, the gas barrier properties become insufficient.
• an anchor coat before the film formation step in order to improve the adhesion between the inorganic vapor deposition film and the resin layer, specifically, for example, to provide a coating step in which an anchor coating agent is coated on at least one surface of the resin layer.
• the anchor coating agent used to form the anchor coat is not particularly limited as long as it is an anchor coating resin that is conventionally used as an undercoat layer when performing vapor deposition on polyester films such as polyethylene terephthalate, but in consideration of environmental issues after biodegradation of the film substrate, it is preferable that the agent is one or more selected from the group consisting of polyester resins, polyurethane resins, polyacrylic resins, polyvinyl alcohol resins, polyolefin resins, and aliphatic polyester resins.
• alcohol-based solvents such as methyl alcohol, ethyl alcohol, or isopropanol, cyclohexane, dimethylformamide, ethyl acetate, water, benzene, toluene, acetone, tetrahydrofuran, dioxane, chloroform, or methyl ethyl ketone can be used, but in terms of adhesion, it is preferable to use one or a mixed solvent of two or more selected from the group consisting of alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropanol, cyclohexane, dimethylformamide, ethyl acetate, and water.
• alcohol-based solvents such as methyl alcohol, ethyl alcohol, or isopropanol, cyclohexane, dimethylformamide, ethyl acetate, and water.
• the thickness of the anchor coat layer formed by coating with such an anchor coat agent is preferably 0.01 to 5 ⁇ m, and more preferably 0.1 to 2 ⁇ m.
• the surface of the film substrate may be subjected to a corona treatment in a conventional manner prior to the film formation step, and at least one surface of the resin layer that has been subjected to the corona treatment may be coated with the anchor coat agent, preferably the corona-treated surface.
• the oxygen gas permeability of the laminate or film (laminated film) is preferably 10 cc/ m2 ⁇ 24 hr ⁇ atm or less, more preferably 7 cc/ m2 ⁇ 24 hr ⁇ atm or less, and even more preferably 4 cc/ m2 ⁇ 24 hr ⁇ atm or less.
• the lower limit of the oxygen gas permeability is not particularly limited, and the smaller the value, the better the oxygen barrier property, so it is preferable.
• the laminate or film (laminated film) has a more sufficient gas barrier function and is particularly suitable for use as, for example, a packaging material.
• the oxygen gas permeability of the laminate or laminate film is measured by the method described in the Examples section below.
• a laminate which is another embodiment of the present invention is a laminate in which a base layer, a vapor-deposited film, and a resin layer are laminated in this order, the resin layer being made of a resin composition containing an aliphatic polyester-based resin (A) containing, as main structural units, repeating structural units derived from an aliphatic diol and repeating structural units derived from an aliphatic dicarboxylic acid, and the aliphatic polyester-based resin (A) contains, as the repeating structural units derived from the aliphatic dicarboxylic acid, at least repeating structural units derived from succinic acid and repeating structural units derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms.
• the resin composition contained in the resin layer in the laminate may be the resin composition described above.
• the vapor-deposited film in the laminate is preferably an inorganic vapor-deposited film, and as the inorganic vapor-deposited film, it is preferable to use the inorganic substances formed in the above-mentioned films.
• the laminate is preferably a vapor deposition film formed on the surface of the resin layer by vapor deposition. In this case, it is preferable to use the resin layer and the inorganic vapor deposition film described above for the film, respectively, as the resin layer and the inorganic vapor deposition film.
• the substrate layer is preferably a fiber or a film, and specific examples thereof include paper, paperboard, cotton nonwoven fabric, rayon nonwoven fabric, polylactic acid film, cellulose nitrate film, cellulose acetate film, cellulose film, polyglycolic acid film, and polyethylene terephthalate film.
• the substrate layer has biodegradability, and specifically, the substrate layer preferably contains a plant-derived component, and more preferably, the substrate layer is composed of a plant-derived component.
• paper, paperboard, pulp nonwoven fabric, cotton nonwoven fabric, rayon nonwoven fabric, polylactic acid film, and cellulose film and in particular, paper, paperboard, polylactic acid film, and cellulose film are preferred.
• a composite film that is biodegradable by blending starch or chitosan with cellulose acetate or regenerated cellulose, which is not biodegradable by itself, can also be used.
• the paper substrate examples include wrapping paper such as kraft paper or pure white roll paper, printing and information paper such as imitation paper, fine paper, medium quality paper, glassine paper, parchment, art paper, or coated paper, processed base paper such as cup base paper or cardboard base paper, paperboard such as Kent paper, Manila cardboard, or coated cardboard, or barrier paper imparted with oxygen barrier properties or water vapor barrier properties by a coating agent such as polyvinyl alcohol (PVOH).
• Nonwoven fabrics such as cotton nonwoven fabrics and rayon nonwoven fabrics are also included in the paper substrate.
• the basis weight (JIS P8124:2011) of these paper substrates varies depending on the paper quality, but is usually 10 to 1000 g/m 2 , and preferably 30 to 700 g/m 2 .
• methods for improving dry strength include the internal addition of dry strength enhancers such as polyacrylamide, cationic starch, or amphoteric starch.
• the amount of dry strength enhancer added is usually 0.01 to 0.3 mass% of bone-dry pulp.
• internal addition refers to a method of adding an additive to the pulp slurry before papermaking.
• beating degree of the pulp before papermaking is also a method of increasing the beating degree of the pulp before papermaking to a freeness of about 450 to 600 ml.
• CSF refers to the Canadian standard freeness commonly used in the papermaking industry.
• NNKP softwood bleached kraft pulp
• the paper base material is hydrophilic, when the laminate comes into contact with water, water may penetrate from the edge of the laminate, causing the base material layer to swell and become puffy or wrinkled, or the layers inside the base material layer may break down and peel off. Therefore, for applications requiring water resistance, it is preferable to improve the sizing degree or wet strength of the paper base material.
• a method for improving the sizing degree includes a method of adding an internal sizing agent such as an alkyl ketene dimer.
• the amount of the internal sizing agent added is usually 0.1 to 0.5% by mass based on the bone dry pulp. In this case, it is also preferable to use aluminum sulfate in combination.
• an internal wet strength enhancer such as polyamide polyamine, polyamide polyamine epichlorohydrin modified product, polyethyleneimine epichlorohydrin modified product, etc.
• the amount of the internal wet strength enhancer added is usually 0.1 to 0.5% by mass based on the bone dry pulp.
• Paper or paperboard is usually blended with a filler, which is called a "filler.”
• a filler which is called a "filler.”
• the blending amount of these fillers is usually 1 to 30% by mass relative to the paper base material.
• inorganic fillers such as talc, kaolin, calcined kaolin, clay, diatomaceous earth, magnesium carbonate, aluminum hydroxide, magnesium sulfate, silica, aluminosilicates, or bentonite, or organic fillers such as polystyrene particles or urea-formaldehyde resin particles, can be appropriately selected and used as necessary.
• organic fillers such as polystyrene particles or urea-formaldehyde resin particles, can be appropriately selected and used as necessary.
• graphite or carbon black may be added to the base layer, or the surface of the base layer may be printed in black.
• Nonwoven fabrics can also be used as the base layer.
• Specific examples include Asahi Kasei's Benliese (registered trademark), which is a hydroentanglement nonwoven fabric made from cotton linters; Oji Kinocloth (registered trademark), which is an airlaid nonwoven fabric made from pulp; Omi Kenshi's Piros (registered trademark), which is a spunlace nonwoven fabric made from rayon; Kuraray's Kuraflex (registered trademark), which is a hydroentanglement nonwoven fabric made from rayon; Unitika's Terramac (registered trademark), which is a spunbond nonwoven fabric made from polylactic acid; and Shinwa's Hibon (registered trademark).
• Films containing plant-derived components can also be used as the substrate layer.
• Specific examples include cellulose acetate-based films such as Celgreen PC-A (registered trademark) manufactured by Daicel Chemical Industries, Ltd. and Lunare ZT (registered trademark) manufactured by Nippon Shokubai Co., Ltd., cellulose-based films such as NatureFlex NP, NPU, NK, and NKR NE series manufactured by Futamura Chemical Co., Ltd., modified starch such as Plantic (registered trademark) HP manufactured by Kuraray Co., Ltd., blend films of starch and synthetic biodegradable polymers such as Materbee (registered trademark) manufactured by Novamont Co., Ltd., Doron CC (trade name) manufactured by Aicello Chemical Co., Ltd., blend films of chitosan, cellulose, and starch, polyglycolic acid film such as Kuredux (registered trademark) manufactured by Kuraray Co., Ltd., and PLA film such as Ecologe (registere
• the substrate layer When manufacturing a laminate by laminating such a substrate layer onto the inorganic vapor deposition film side of the resin layer, the substrate layer may be bonded to the inorganic vapor deposition film by, for example, a urethane adhesive or a polyester adhesive. Alternatively, the layers may be bonded by extrusion lamination.
• the laminate may be formed by laminating together a substrate layer, a vapor deposition film, and a film substrate made of a resin composition, but may also have other layers as necessary.
• the other layers There are no particular limitations on the other layers as long as they do not impair the objectives of the present invention (gas barrier properties, thin film properties, etc.), and examples of such layers include a printing layer or an adhesive layer.
• the mass ratio of the aliphatic polyester resin (A) to the total mass of the base layer and the resin layer is preferably 5 to 80 mass %, and more preferably 10 to 70 mass %.
• the mass proportion of the aliphatic polyester resin (A) is equal to or greater than the lower limit of the above range, sufficient heat sealability can be obtained when used as a packaging material, and when it is equal to or less than the upper limit of the above range, sufficient rigidity can be obtained.
• the total thickness of the laminate is preferably 10 to 300 ⁇ m, and more preferably about 20 to 250 ⁇ m.
• the water vapor transmission rate (moisture permeability) of the laminate or film (laminated film) is preferably 10 g/m 2 ⁇ 24 h or less, more preferably 7 g/m 2 ⁇ 24 h or less, and even more preferably 4 g/m 2 ⁇ 24 h or less.
• the lower limit of the water vapor transmission rate is not particularly limited, and the smaller the value, the better the oxygen barrier property, so it is preferable.
• the laminate or film (laminated film) When the water vapor transmission rate (moisture permeability) of the laminate or film (laminated film) satisfies the above conditions, the laminate or film (laminated film) has more sufficient moisture resistance and is particularly suitable for use as, for example, a packaging material.
• the water vapor transmission rate (moisture permeability) can be measured in accordance with JIS Z0208:1976, and the measurement conditions are condition B (temperature 40 ⁇ 0.5°C, relative humidity 90 ⁇ 2%).
• the oxygen gas permeability of the laminate or film (laminated film) is preferably 10 cc/ m2 ⁇ 24 hr ⁇ atm or less, more preferably 7 cc/ m2 ⁇ 24 hr ⁇ atm or less, and even more preferably 4 cc/ m2 ⁇ 24 hr ⁇ atm or less.
• the lower limit of the oxygen gas permeability is not particularly limited, and the smaller the value, the better the oxygen barrier property, so it is preferable.
• the laminate or film (laminated film) has a more sufficient gas barrier function and is particularly suitable for use as, for example, a packaging material.
• the oxygen gas permeability can be measured using an oxygen permeability measuring device at a temperature of 23°C and a humidity of 75% RH in accordance with JIS K7126-2:2006.
• an "OX-TRAN" product name, manufactured by Mocon, USA was used as the oxygen permeability measuring device.
• the laminate and film (laminated film) according to the present disclosure have gas barrier properties while being degradable in the natural environment, and therefore can be suitably used as packaging materials.
• they can be excellent in formability, transparency, surface properties, mechanical properties, etc., and therefore can be suitably used in a wide range of applications, such as food packaging materials, pharmaceutical packaging materials, packaging materials for liquids, powders, or solids such as miscellaneous goods, agricultural materials, or construction materials, particularly in disposable applications.
• preferred applications include agricultural mulch films, tunnel films, greenhouse films, sunshades, weed control sheets, ridge sheets, germination sheets, forestry fumigation sheets, binding tapes containing flat yarns or the like, diaper back sheets, packaging sheets, shopping bags, plastic bags, garbage bags, draining bags, compost bags, oily food packaging, dried food packaging, livestock product packaging, seafood product packaging, beverage and liquid food packaging, dried confectionery packaging, snack food packaging, instant noodle packaging, retort food packaging, chilled and frozen food packaging, black tea, green tea, coffee and the like packaging, supplement packaging, cosmetic packaging, electronic component packaging, and optical component packaging.
• Another embodiment of the present invention is a packaging material having the film or laminate described above, the particular uses of which are as described above. Furthermore, as explained so far in this specification, by using an aliphatic polyester-based resin (A) in a resin layer of a film (laminated film) having a resin layer and an inorganic vapor deposition film provided on at least one surface of the resin layer, it is possible to obtain a laminated film in which the resin layer and the inorganic vapor deposition film have high adhesion and in which biodegradability (home compostability, marine biodegradability) is further improved.
• A aliphatic polyester-based resin
• an aliphatic polyester resin (A) in the resin layer of a laminate in which a base layer, a vapor-deposited film, and a resin layer are laminated in this order, a laminate can be obtained in which the vapor-deposited film and the resin layer have high adhesion and the biodegradability (home compostability, marine biodegradability) is further improved.
• the present invention also provides a new use of the aliphatic polyester resin (A) in resin layers and films on which inorganic vapor-deposited films are formed.
• Preparation of polycondensation catalyst 343.5 parts by weight of magnesium acetate tetrahydrate was placed in a reactor equipped with a stirrer, and 1434 parts by weight of anhydrous ethanol (purity 99% by weight or more) was added. 218.3 parts by weight of ethyl acid phosphate (mixture weight ratio of monoester and diester is 45:55) was added and stirred at 23°C. After confirming that magnesium acetate was completely dissolved, 410.0 parts by weight of tetra-n-butyl titanate was added. Stirring was continued for another 10 minutes to obtain a homogeneous mixed solution. This mixed solution was concentrated under reduced pressure while controlling the temperature at 60°C or less.
• Aliphatic polyester resin A-1 A reaction vessel equipped with a stirrer, a nitrogen inlet, a heater, a thermometer, and a pressure reducing port was charged with 57.8 parts by weight of succinic acid, 12.3 parts by weight of sebacic acid, 64.4 parts by weight of 1,4-butanediol, 0.125 parts by weight of trimethylolpropane, and 0.60 parts by weight of the catalyst solution as raw materials.
• the molar ratio of succinic acid to sebacic acid was 89:11, and the proportion of the substance amount of 1,4-butanediol to the total substance amount of succinic acid and sebacic acid was 1.30.
• Nitrogen gas was introduced into the vessel while stirring the contents of the vessel, and the system was placed under a nitrogen atmosphere by vacuum replacement. Next, the raw materials were dissolved at 160°C, and after confirming that the raw materials were completely dissolved and the distillation part temperature reached 50°C, the temperature was raised from 160°C to 230°C over 1 hour while stirring the system, and the esterification reaction was continued for 1 hour at 230°C and normal pressure. A catalyst solution was added 5 minutes before the end of the esterification reaction.
• Aliphatic polyester resin A-2 (amount of succinic acid units in the total dicarboxylic acid unit amount: 74 mol%, amount of sebacic acid units: 26 mol%, MFR: 5.0 g/10 min, melting point: 85° C.) was produced in the same manner as in Production Example of Aliphatic Polyester Resin A-1, except that 44.9 parts by weight of succinic acid, 27.1 parts by weight of sebacic acid, 60.2 parts by weight of 1,4-butanediol, 0.125 parts by weight of trimethylolpropane, and 0.60 parts by weight of catalyst solution were used and the molar ratio of succinic acid to sebacic acid was changed to 74:26.
• Aliphatic polyester resin A-3 Aliphatic polyester resin A-3 (succinic acid unit amount in total dicarboxylic acid unit amount: 95 mol%, sebacic acid unit amount: 5 mol%, MFR: 5.0 g/10 min, melting point: 108° C.) was produced in the same manner as in Production Example of Aliphatic Polyester Resin A-1, except that 62.8 parts by weight of succinic acid, 5.4 parts by weight of sebacic acid, 65.5 parts by weight of 1,4-butanediol, 0.125 parts by weight of trimethylolpropane, and 0.60 parts by weight of catalyst solution were used and the molar ratio of succinic acid to sebacic acid was 95:5.
• PBS "BioPBS (registered trademark) FZ91PM” manufactured by PTTMCC Biochem (amount of succinic acid units in total amount of dicarboxylic acid units: 100 mol%, MFR: 5.0 g/10 min, melting point: 115°C)
• PBSA "BioPBS (registered trademark) FD92PM” manufactured by PTTMCC Biochem (amount of succinic acid units in total amount of dicarboxylic acid units: 74 mol%, amount of adipic acid units: 26 mol%, MFR: 5.0 g/10 min, melting point: 84°C)
• PHBH Kaneka Biodegradable Biopolymer Green Planet (registered trademark) X131A manufactured by Kaneka Corporation (3HB/3HH molar ratio: 94/6, MFR: 6 g/10 min, melting point: 140° C.)
• melt flow rate (MFR) The melt flow rate (MFR) of each of the above-mentioned resins was measured at a temperature of 190° C. and a pressure of 2.16 kgf using a melt indexer based on JIS K7210-1:2014. The unit is g/10 min.
• the heat seal strength was determined based on the heat seal strength test (7.4) specified in JIS Z1707:2019.
• the test piece was a flat portion of the resin layer having a thickness of 30 ⁇ m, cut into a length and width of 15 cm, one end of which was heat sealed with a heat sealer so that the resin layer portions were aligned, and cut into a rectangular shape having a width of 15 mm.
• the heat sealing was performed using a one-sided heating bar sealer with a seal bar width of 5 mm at a sealing temperature of 120° C., a sealing pressure of 0.2 MPa, and a sealing time of 1 second.
• the heat seal strength was measured by a Tensilon universal testing machine at a peel angle of 180 degrees and a pulling speed of 300 mm/min, and was determined as the load (N/15 mm) at which the sealed portion peeled or broke.
• the evaluation criteria were as follows: Rank A (good): 10N/15mm or more Rank B (not good): less than 10N/15mm
• the bio-based carbon content of each polyester resin was evaluated in accordance with ASTM D6866. Specifically, the composition was burned, carbon dioxide was collected, and the carbon atoms in the composition were recovered as graphite by reducing the carbon dioxide with hydrogen and a catalyst. Next, the carbon isotope ratio was measured using an accelerator mass spectrometer. Since 14 C exists in the atmosphere at a certain rate, the same rate of 14 C is also contained in carbon derived from biomass (bio-based carbon). On the other hand, since 14 C decreases with a half-life of 5730 years, carbon derived from fossil resources does not contain 14 C. Therefore, the bio-based carbon content was calculated by calculating the ratio of 14 C in the sample to the standard ratio of 14 C contained in the modern atmosphere.
• Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-6 As raw materials for the aliphatic polyester film (resin layer, film for forming an inorganic vapor deposition film), the raw materials shown in Table 1 were blended in the ratios shown in Table 1, extruded into a strand shape using a twin-screw extruder with a screw diameter of ⁇ 30 mm at a kneading temperature of 140° C., and pelletized using a pelletizer. The obtained resin pellets were used to produce an aliphatic polyester film with a thickness of 30 ⁇ m at 150° C. and a blow ratio of 2.5 using an inflation film molding machine with a screw diameter of ⁇ 40 mm.
• the obtained film was subjected to the above-mentioned evaluations 1 to 5 and evaluations 8 to 11, and each physical property and characteristic was measured and evaluated.
• the evaluations 2 to 5 and 8 to 11 were not performed.
• Example 2-1 A single-layer film having a thickness of 30 ⁇ m was prepared in the same manner as in Example 1-1. Next, in order to enhance adhesion, the surface coated with the anchor coating agent was subjected to a corona treatment immediately before the film was wound up by a winder, and an anchor coating agent consisting of 1 part by mass of a copolymer polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.), 0.1 part by mass of an isocyanate compound (hexamethylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.), 25 parts by mass of toluene, and 25 parts by mass of methyl ethyl ketone was applied to the corona-treated side prior to deposition so that the film thickness after drying was 0.2 ⁇ m, and then dried at 60° C. No wrinkles or the like were generated in the resulting aliphatic polyester film.
• a copolymer polyester resin Vylon 200 manufactured by Toyobo Co., Ltd.
• the anchor coat-treated surface of the obtained aliphatic polyester film was continuously subjected to deposition treatment under a vacuum of 1 ⁇ 10 ⁇ 4 hPa using an electron beam heating type vacuum deposition machine (manufactured by Rayboldt Co., Ltd.) to form an aluminum deposition film having a thickness of 60 nm and made of aluminum with a purity of 99.9 mol%, thereby obtaining a laminated film.
• an electron beam heating type vacuum deposition machine manufactured by Rayboldt Co., Ltd.
• a substrate made of a 20 ⁇ m thick cellulose film (product name: Hakusan Cellophane #300; manufactured by Rengo Co., Ltd.) was fixed via an adhesive layer onto the vapor deposition film of the laminated film prepared in the same manner as above to obtain a laminate according to this example.
• the obtained laminate was subjected to the above evaluations 6 to 9 and the following evaluation 12.
• the load when the vapor-deposited film and the substrate were peeled off at a peel angle of 180° and a tensile speed of 300 mm/min was measured with a Tensilon universal testing machine, and the value (gf/15 mm) was recorded.
• Example 2-1 A laminate film and a laminate were produced and evaluated in the same manner as in Example 2-1, except that a single-layer film having a thickness of 30 ⁇ m, which was produced in the same manner as in Comparative Example 1-3, was used as the single-layer film.
• Example 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 are shown in Table 2.
• the evaluation results for Example 2-1 and Comparative Example 2-1 are shown in Table 3.
• the laminates and films (laminate films) according to the present disclosure have a high degree of biodegradability at room temperature and excellent marine biodegradability, and have extremely high biodegradability and extremely low moisture permeability and oxygen gas permeability.
• the resin layer and the film for forming an inorganic vapor deposition film according to the present disclosure have a high wetting tension (surface tension) and a surface with a small arithmetic mean height Ra (high smoothness), and therefore have excellent adhesion to the vapor deposition film.
• the resin layer or film for forming an inorganic vapor deposition film according to the present disclosure can reduce moisture permeability and oxygen gas permeability even with a small layer structure by providing a vapor deposition film on at least one surface, and can be particularly suitable for use as packaging materials, particularly food packaging materials and pharmaceutical packaging materials.

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