Laminate, film, film production method, and film for forming inorganic vapor-deposited film

Abstract

The present invention provides a laminate having excellent adhesion between a resin layer and an inorganic vapor-deposited film, and excellent biodegradability of the resin layer, especially biodegradability at room temperature and marine biodegradability.　The laminate has a base material layer, a vapor-deposited film, and a resin layer in the stated order. The resin layer includes a first aliphatic polyester resin (A). The first aliphatic polyester resin (A) includes, 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 at least includes a repeating structural unit A21 derived from succinic acid and a repeating structural unit A22 derived from a C9-36 aliphatic dicarboxylic acid.

Description

Laminate, film, film manufacturing method, and film for forming inorganic vapor deposition film

[0001] The present invention relates to a laminate, a film, a method for producing a film, and a film for forming an inorganic vapor-deposited film.

[0002] In recent years, concerns about ecosystem and environmental pollution due to the disposal of plastic products in the ocean, etc., have become apparent. For example, in Europe, regulations and laws are being enacted that prohibit the use of disposable plastic shopping bags in retail stores and disposable plastic containers such as cups and plates, and various regulations are being enacted around the world from the perspective of preventing environmental pollution, etc. Recently, there has been a demand for products made from biodegradable plastics, such as not only plastic products that can be composted in ordinary households (home compostable products), but also marine biodegradable plastic products, which decompose in the ocean if plastic products are discharged into the ocean.

[0003] Conventionally, known biodegradable plastics (resins) 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). Furthermore, known resins that are biodegradable to a certain extent, particularly in the ocean, include polybutylene succinate / adipate (hereinafter abbreviated as PBSA) and polyhydroxyalkanoate (hereinafter abbreviated as PHA). 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).

[0004] 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.

[0005] Furthermore, Patent Document 2 discloses a molded article including a laminate in which a vapor-deposited layer containing an inorganic material is provided on at least one surface of a resin layer using a poly(3-hydroxybutyrate)-based resin, and shows that forming the vapor-deposited layer on a surface having a surface tension of 36 mN / m or more improves the adhesion and gas barrier properties of the vapor-deposited layer.

[0006] 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 composed of a specific aliphatic diol and an aliphatic dicarboxylic acid, and further discloses a laminate or packaging material in which the film is laminated to a substrate, and shows that the film can be degradable in soil or in the ocean while also providing barrier properties.

[0007] Japanese Patent Application Laid-Open No. 7-195646 International Publication No. 2020-262619 Japanese Patent Application Laid-Open No. 2022-31161

[0008] In recent years, social trends toward stronger environmental protection, particularly environmental pollution caused by the disposal of used plastic products (especially the impact of microplastics caused by the disposal of used plastic products in the ocean), have led to a demand for biodegradable resins that are not only partially biodegradable but also completely biodegradable. Furthermore, in terms of the biodegradation environment, not only biodegradability in a relatively high-temperature (58°C or higher) aerobic composting environment (soil) but also biodegradability in aerobic composting environment (soil) at room temperature (28°C) and high biodegradability in the ocean are required. If a resin exhibits not only room-temperature biodegradability but also marine biodegradability, for example, films made of biodegradable resins can be disposed of as home compost after use, and furthermore, by biodegrading in the ocean, the adverse impact of microplastics on marine life can be eliminated.

[0009] The technology described in Patent Document 1 allows biodegradation to proceed under conditions that are relatively favorable for biodegradation, but biodegradability in aerobic compost at room temperature, in soil environments, and in the sea is not sufficient.

[0010] The vapor-deposited films described in Patent Documents 2 and 3 can ensure degradability by depositing vapor onto a resin film that is biodegradable in aerobic compost at room temperature, in soil environments, and in the sea, but the adhesion of the inorganic vapor-deposited film is not satisfactory.

[0011] The present invention was made in consideration of the problems inherent in the prior art, and aims to provide a laminate or film that exhibits excellent adhesion between a resin layer and an inorganic vapor-deposited film, as well as excellent biodegradability, particularly biodegradability at room temperature and marine biodegradability. Another object of the present invention is to provide a method for producing a film that exhibits excellent adhesion between a resin layer and an inorganic vapor-deposited film, as well as excellent biodegradability. A further object of the present invention is to provide a film for forming an inorganic vapor-deposited film that exhibits excellent adhesion to an inorganic vapor-deposited film and excellent biodegradability. A still further object of the present invention is to provide a new use for a specific resin that exhibits excellent biodegradability.

[0012] The gist of the present invention lies in the following [1] to

[56] .

[0013] [1] A laminate having, in this order, a substrate layer, a vapor-deposited film, and a resin layer, wherein the resin layer contains a first aliphatic polyester resin (A), wherein 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, and wherein 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. [2] The laminate according to [1], wherein the repeating structural unit A22 is a repeating structural unit derived from an aliphatic dicarboxylic acid having 9 to 13 carbon atoms. [3] The laminate according to [1] or [2], wherein the repeating structural unit A22 is a repeating structural unit derived from sebacic acid. [4] The laminate according to any one of [1] to [3], wherein the content (A22 / A2) of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 in the first aliphatic polyester resin (A) is 1 mol% or more and 50 mol% or less. [5] The laminate according to [4], wherein the content (A22 / A2) is 5 mol% or more and 40 mol% or less. [6] The laminate according to [4], wherein the content (A22 / A2) is 7 mol% or more and 40 mol% or less. [7] The laminate according to [4], wherein the content (A22 / A2) is 10 mol% or more and 30 mol% or less. [8] The laminate according to [4], wherein the content (A22 / A2) is 11 mol% or more and 30 mol% or less.[9] The repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester resin (A) is 95 mol% or more and 100 mol% or less, the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol% or more and 30 mol% or less, the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol% or more and 89 mol% or less, and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol% or more and 20 mol% or less, and The laminate according to any one of [1] to [9], wherein the content ratio (A22 / A2) / the content ratio (A23 / A2) exceeds 1.

[10] The laminate according to any one of [1] to [9], wherein the repeating structural unit A1 comprises 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 from 95 mol% to 100 mol%; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22 / A2) is from 11 mol% to 30 mol%; the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21 / A2) is from 50 mol% to 89 mol%; and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is from 0 mol% to less than 11 mol%.

[11] The laminate according to any one of [1] to

[10] , wherein the first aliphatic polyester resin (A) contains polybutylene succinate sebacate (PBSSe).

[12] The laminate according to any one of [1] to

[10] , wherein the first aliphatic polyester resin (A) is polybutylene succinate sebacate (PBSSe).

[13] The laminate according to any one of [1] to

[12] , wherein a content of the first aliphatic polyester resin (A) relative to the resin layer is 10% by mass or more and 100% by mass or less.

[14] The resin layer further comprises 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), wherein 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), and the third aliphatic polyester 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 first aliphatic polyester resin (A).

[15] The laminate according to any one of [1] to

[14] , wherein the resin layer further comprises a polyhydroxyalkanoate (C), which is different from the first aliphatic polyester resin (A).

[16] The laminate according to

[15] , wherein the polyhydroxyalkanoate (C) comprises a repeating structural unit C11 derived from 3-hydroxybutyrate, and the proportion of the number of moles of the repeating structural unit C11 relative to the total number of moles of structural units constituting the polyhydroxyalkanoate (C) is 70 mol % or more.

[17] The laminate according to

[15] , wherein the content of the first aliphatic polyester resin (A) in the resin layer ((A) / ((A)+(C))) is 70 mass% or more and less than 100 mass% with respect to the total mass of the first aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).

[18] The laminate according to

[14] , wherein the content of the second aliphatic polyester resin (B1) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [(B1) / ((A)+(B1)+(B2)+(B3)+(C))] is 95 mass% or less.

[19] The laminate according to

[14] , wherein the total content of the aliphatic-aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) relative to the sum of the mass of the first 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 [((B2) + (B3)) / ((A) + (B1) + (B2) + (B3) + (C))] is 50 mass% or less.

[20] The laminate according to any one of [1] to

[19] , wherein the proportion of the total number of moles of repeating structural units derived from succinic acid in all polyester resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester resins contained in the resin layer is 50 mol% or more and 99 mol% or less.

[21] The laminate according to any one of [1] to

[20] , wherein the ratio of the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer is 1 mol% or more and 50 mol% or less.

[22] The laminate according to any one of [1] to

[21] , wherein the content of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer is 5 mol% or more and 40 mol% or less to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer.

[23] The laminate according to any one of [1] to

[22] , wherein the resin layer has a bio-based carbon content of 25% or more and a crystallization half-time at a temperature of 50°C of 0.35 minutes or more.

[24] The laminate according to any one of [1] to

[23] , wherein the resin layer has an alkali metal content of 6.0 ppm by mass or less.

[25] The laminate according to any one of [1] to

[24] , wherein the base layer contains a plant-derived component.

[26] The laminate according to any one of [1] to

[25] , wherein 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 composite of silicon oxide and aluminum oxide.

[27] A film having a resin layer and a vapor-deposited film provided on at least one surface of the resin layer, wherein the resin layer contains a first aliphatic polyester resin (A), and 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, and 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.

[28] The film according to

[27] , wherein the repeating structural unit A22 is a repeating structural unit derived from an aliphatic dicarboxylic acid having 9 to 13 carbon atoms.

[29] The film according to

[27] or

[28] , wherein the repeating structural unit A22 is a repeating structural unit derived from sebacic acid.

[30] The film according to any one of

[27] to

[29] , wherein the content (A22 / A2) of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 in the first aliphatic polyester resin (A) is 1 mol% or more and 50 mol% or less.

[31] The film according to

[30] , wherein the content (A22 / A2) is 5 mol% or more and 40 mol% or less.

[32] The film according to

[30] , wherein the content (A22 / A2) is 7 mol% or more and 40 mol% or less.

[33] The film according to

[30] , wherein the content (A22 / A2) is 10 mol% or more and 30 mol% or less.

[34] The film according to

[30] , wherein the content (A22 / A2) is 11 mol% or more and 30 mol% or less.

[35] The repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol; the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester resin (A) is 95 mol% or more and 100 mol% or less; the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol% or more and 30 mol% or less; the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol% or more and 89 mol% or less; and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol% or more and 20 mol% or less; and The film according to any one of

[27] to

[34] , wherein the content ratio (A22 / A2) / the content ratio (A23 / A2) exceeds 1.

[36] The film according to any one of

[27] to

[34] , wherein 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 from 95 mol % to 100 mol %; the content of the repeating structural unit A22 relative to the number of moles of the repeating structural unit A2 (A22 / A2) is from 11 mol % to 30 mol %; the content of the repeating structural unit A21 relative to the number of moles of the repeating structural unit A2 (A21 / A2) is from 50 mol % to 89 mol %; and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is from 0 mol % to less than 11 mol %.

[37] The film according to any one of

[27] to

[36] , wherein the first aliphatic polyester resin (A) comprises polybutylene succinate sebacate (PBSSe).

[38] The film according to any one of

[27] to

[36] , wherein the first aliphatic polyester resin (A) is polybutylene succinate sebacate (PBSSe).

[39] The film according to any one of

[27] to

[38] , wherein the content of the first aliphatic polyester resin (A) relative to the resin layer is 10% by mass or more and 100% by mass or less.

[40] The resin layer further comprises 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), wherein 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), and the third aliphatic polyester 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 aliphatic polyester resin (A).

[41] The film according to any one of

[27] to

[40] , wherein the resin layer further comprises a polyhydroxyalkanoate (C), and the polyhydroxyalkanoate (C) is different from the first aliphatic polyester resin (A).

[42] The film according to

[41] , wherein the polyhydroxyalkanoate (C) comprises a repeating structural unit C11 derived from 3-hydroxybutyrate, and the proportion of the number of moles of the repeating structural unit C11 relative to the total number of moles of structural units constituting the polyhydroxyalkanoate (B) is 70 mol % or more.

[43] The film according to

[41] or

[42] , wherein the content of the first aliphatic polyester resin (A) in the resin layer ((A) / ((A)+(C))) is 70 mass% or more and less than 100 mass% with respect to the total mass of the first aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).

[44] The film according to

[40] , wherein the content of the second aliphatic polyester resin (B1) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [(B1) / ((A)+(B1)+(B2)+(B3)+(C))] is 95 mass% or less.

[45] The film according to

[40] , wherein the total content of the aliphatic-aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) relative to the sum of the mass of the first 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 [((B2) + (B3)) / ((A) + (B1) + (B2) + (B3) + (C)]] is 50 mass% or less.

[46] The film according to any of

[27] to

[45] , wherein the proportion of the total number of moles of repeating structural units derived from succinic acid in all polyester resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester resins contained in the resin layer is 50 mol% or more and 99 mol% or less.

[47] The film according to any one of

[27] to

[46] , wherein the ratio of the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer is 1 mol% or more and 50 mol% or less.

[48] The film according to any one of

[27] to

[47] , wherein the content of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer is 5 mol% or more and 40 mol% or less to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer.

[49] The film according to any one of

[27] to

[48] , wherein the content of alkali metals in the resin layer is 6.0 ppm by mass or less.

[50] The film according to any one of

[27] to

[49] , wherein 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 composite of silicon oxide and aluminum oxide.

[51] A method for producing a film having a resin layer and an inorganic vapor-deposited film provided on at least one surface of the resin layer, comprising a film-forming step of forming an inorganic vapor-deposited film on at least one surface of the resin layer, wherein the resin layer comprises a first aliphatic polyester resin (A) containing, 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 units A2 include 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.

[52] The method for producing a film according to

[51] , including, prior to the film-forming step, a corona treatment step of corona-treating the surface of the resin layer on which the inorganic vapor-deposited film is to be formed, and a coating step of coating the surface that has been subjected to the corona treatment step with an anchor coating agent.

[53] A film for forming an inorganic vapor-deposited film, comprising a first aliphatic polyester-based resin (A), the first aliphatic polyester-based resin (A) comprising, 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 comprising 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-deposited film having a bio-based carbon content of 25% or more and a crystallization half time at a temperature of 50°C of 0.35 minutes or more.

[54] The film for forming an inorganic vapor-deposited film according to

[53] , wherein the arithmetic mean height of a roughness curve (arithmetic mean roughness) Ra measured in at least one of the MD and TD directions on at least one surface of the film according to Japanese Industrial Standards (JIS) B0601:2001 is 0.25 μm or less.

[55] Use of a first aliphatic polyester resin (A) in a resin layer to improve the biodegradability of a film having a resin layer and an inorganic vapor-deposited film provided on at least one surface of the resin layer, wherein the first aliphatic polyester 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.

[56] Use of a first aliphatic polyester-based resin (A) in a resin layer to improve the biodegradability of a laminate having a base layer, a vapor-deposited film, and a resin layer laminated in this order, 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 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.

[0014] According to the present invention, it is possible to provide a laminate and a film that have excellent adhesion between a resin layer and an 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 a resin layer and an 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 an 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.

[0015] Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description and can be modified as desired without departing from the spirit and scope of the present invention. In this specification, when a numerical value or physical property value is enclosed before and after the prefix "~", the values ​​before and after the prefix, i.e., the upper and lower limits, which are the endpoints, are included. Furthermore, when a numerical range is described in stages, any combination of the upper and lower limits of each numerical range is also disclosed. Furthermore, in this specification, the expression "A or B" can be interpreted as "at least one selected from the group consisting of A and B." Furthermore, in this specification, 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. Although multiple embodiments are described in this specification, various conditions in each embodiment can be applied to each other to the extent applicable. Furthermore, in this specification, "mass %" and "wt %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0016] As a result of extensive research into achieving the above-mentioned object, the present inventors have found that a laminate or film that contributes to achieving the above-mentioned object can be obtained by incorporating into the resin layer a first aliphatic polyester 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 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 that this first aliphatic polyester resin (A) contains, as the repeating structural unit A2 derived from the aliphatic dicarboxylic acid, a repeating structural unit derived from a specific aliphatic dicarboxylic acid, and have thus completed the present invention. <Laminate> 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, wherein the resin layer comprises a first aliphatic polyester resin (A), wherein the first aliphatic polyester resin (A) 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 wherein the repeating structural unit A2 derived from an aliphatic dicarboxylic acid 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. <Film> A film having a laminate structure according to one embodiment of the present invention (hereinafter sometimes simply referred to as "film" or "laminated film") has a resin layer and a vapor-deposited film provided on at least one surface of the resin layer, wherein the resin layer comprises a first aliphatic polyester resin (A), and the first aliphatic polyester resin (A) 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. The laminate and film exhibit excellent biodegradability because the resin layer comprises the first aliphatic polyester resin (A) (hereinafter sometimes simply referred to as "aliphatic polyester resin (A)" or "polyester resin (A)"), which has excellent room temperature biodegradability (home compostability) and marine biodegradability.The resin layer also has a high surface wetting tension, i.e., a high surface tension. Furthermore, the resin layer exhibits a low surface roughness, for example, the arithmetic mean height (arithmetic mean roughness) Ra of the roughness curve according to Japanese Industrial Standards (JIS) B0601:2001. That is, the surface smoothness is increased. As a result, the resin layer exhibits excellent adhesion to a vapor-deposited film. The inventors speculate that the reason why a resin layer containing an aliphatic polyester-based resin (A) exhibits a high surface wetting tension and a low surface roughness compared to resin layers containing other biodegradable resins is as follows: The repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms contained in the aliphatic polyester-based resin (A) has a longer main chain than the repeating structural unit derived from an aliphatic dicarboxylic acid in aliphatic polyester-based resins used in conventional laminates and films in which an inorganic vapor-deposited film is applied to a resin layer. Therefore, the aliphatic polyester resin (A) has a relatively low crystallinity, which is thought to result in a smaller surface roughness and a smoother resin layer. Furthermore, the relatively low crystallinity of the aliphatic polyester resin (A) makes it difficult for low-molecular-weight components to bleed out onto the surface of the resin layer. As a result, the surface tension of the resin layer is thought to be higher. Therefore, a polyester film containing an aliphatic polyester resin (A) that can form 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 the surface, making it particularly suitable for forming an inorganic vapor deposition film on the surface, and can be used as a polyester film for forming an inorganic vapor deposition film (hereinafter simply referred to as a "film for forming an inorganic vapor deposition film"). Unless otherwise specified, all matters relating to the resin layer disclosed hereinafter in this specification are applicable to all of the laminates, films (laminated films), and films for forming inorganic vapor deposition films according to the present invention.

[0017] In this specification, an aliphatic diol refers to a compound in which two hydroxyl groups are bonded to an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is usually a straight-chain aliphatic hydrocarbon group, but may have a branched structure, a cyclic structure, or a plurality of such structures. Also, an aliphatic dicarboxylic acid refers to a compound in which two carboxyl groups are bonded to an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is usually a straight-chain aliphatic hydrocarbon group, but may have a branched structure, a cyclic structure, or a plurality of such structures.

[0018] Furthermore, the aliphatic polyester resin (A) is a polymer having repeating structural units, and each repeating structural unit is also referred to as a compound unit corresponding to the compound from which the repeating structural unit is derived. For example, a repeating structural unit derived from an aliphatic diol is also referred to as an "aliphatic diol unit," and a repeating structural unit derived from an aliphatic dicarboxylic acid is also referred to as an "aliphatic dicarboxylic acid unit." Furthermore, in the present invention, the repeating structural unit A1 derived from an aliphatic diol refers to a repeating structural unit corresponding to the aliphatic diol, i.e., a repeating structural unit formed by the reaction of two hydroxyl groups possessed by the aliphatic diol. Furthermore, the repeating structural unit A2 derived from an aliphatic dicarboxylic acid refers to a repeating structural unit corresponding to the aliphatic dicarboxylic acid, i.e., a repeating structural unit formed by the reaction of two carboxy groups possessed by the aliphatic dicarboxylic acid. The "repeating structural unit A21 derived from succinic acid" refers to a "structural unit corresponding to succinic acid," i.e., a structural unit formed by the reaction of two carboxy groups possessed by succinic acid. Furthermore, the term "repeating structural unit A22 derived from an aliphatic dicarboxylic acid having 9 to 36 carbon atoms" refers to a "structural unit corresponding to an aliphatic dicarboxylic acid having 9 to 36 carbon atoms," i.e., a structural unit formed by the reaction of two carboxy groups possessed by an aliphatic dicarboxylic acid having 9 to 36 carbon atoms. The term "main structural unit" in the aliphatic polyester resin (A) generally refers to a structural unit that accounts for 80 mol% or more of the structural unit in the aliphatic polyester resin (A). When no structural units other than the main structural unit are contained, that structural unit may account for 100 mol%. More specifically, having the aliphatic diol unit A1 and the aliphatic dicarboxylic acid unit A2 as 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 of the total moles of the structural units of the aliphatic polyester resin (A). In this specification, the number of moles of the repeating structural units in the aliphatic polyester resin (A) is counted with the smallest ester unit of the aliphatic polyester resin (A) as 1 mole.This also applies to 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).

[0019] The resin layer according to the present invention can be formed from a resin composition containing an aliphatic polyester resin (A). [Resin Composition] <Aliphatic Polyester Resin (A)> The aliphatic polyester resin (A) contains aliphatic diol units A1 and aliphatic dicarboxylic acid units A2 as main structural units. The aliphatic dicarboxylic acid units A2 contain at least succinic acid units A21 and aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms. From the viewpoint of heat resistance, the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms are preferably aliphatic dicarboxylic acid units having 9 to 13 carbon atoms, and particularly preferably aliphatic dicarboxylic acid units having 10 carbon atoms, specifically, for example, sebacic acid units. On the other hand, 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 preferably contains a repeating structural unit A11 derived from an aliphatic diol having from 2 to 10 carbon atoms, and the aliphatic diol unit A11 is particularly preferably an aliphatic diol unit having from 4 to 6 carbon atoms. Specific examples of such aliphatic diol units A11 include ethylene glycol units, 1,3-propanediol units, 1,4-butanediol units, and 1,4-cyclohexanedimethanol units. Of these, it is particularly preferable that the aliphatic diol unit A11 is a repeating structural unit A11 derived from 1,4-butanediol, i.e., 1,4-butanediol units A11. The resin composition (resin layer) may contain one type of aliphatic polyester resin (A) alone, or may contain two or more types.

[0020] The content of the aliphatic dicarboxylic acid unit 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 structural 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. That is, the content of the aliphatic dicarboxylic acid unit A2 in the aliphatic polyester resin (A), based on the total number of moles of the repeating structural units constituting the aliphatic polyester resin (A) (100 mol%), is preferably 25 mol% or more and 75 mol% or less, particularly preferably 30 mol% or more and 70 mol% or less, even more preferably 35 mol% or more and 65 mol% or less, even more preferably 40 mol% or more and 60 mol% or less, and particularly preferably 45 mol% or more and 55 mol% or less.

[0021] 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 structural 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. That is, the content of the aliphatic diol unit A1 in the aliphatic polyester resin (A), based on the total number of moles of repeating structural units constituting the aliphatic polyester resin (A) (100 mol%), is preferably 25 mol% or more and 75 mol% or less, particularly preferably 30 mol% or more and 70 mol% or less, even more preferably 35 mol% or more and 65 mol% or less, still more preferably 40 mol% or more and 60 mol% or less, and particularly preferably 45 mol% or more and 55 mol% or less.

[0022] (1) Content of each structural unit in aliphatic polyester resin (A) The content of succinic acid units A21 in the aliphatic polyester resin (A) is not particularly limited. However, 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. 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. That is, based on the total number of moles of the aliphatic dicarboxylic acid units A2 in the aliphatic polyester resin (A), 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 units A22 having 9 to 36 carbon atoms in the aliphatic polyester resin (A) is not particularly limited, but from the viewpoints of the surface smoothness, biodegradation rate, and moldability of the resin layer, the content of the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms in the aliphatic dicarboxylic acid units A2 in the aliphatic polyester resin (A) (A22 / A2) 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. Also, 50 mol% or less is preferred, 40 mol% or less is particularly preferred, and 30 mol% or less is more preferred.That is, based on the total number of moles of the aliphatic dicarboxylic acid units A22 in the aliphatic polyester resin (A), the content of the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms (A22 / A2) 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. However, from the viewpoint of heat resistance, the content of the aliphatic diol units A11 having 2 to 10 carbon atoms (A11 / A1) is preferably 90 mol % or more and 100 mol % or less, and particularly preferably 95 mol % or more and 100 mol % or less, based on the total number of moles of the aliphatic diol units A1 in the aliphatic polyester resin (A).

[0023] (2) Content of each dicarboxylic acid unit in all polyester resins contained in the resin composition From the viewpoint of the biodegradability, surface smoothness, and moldability of the resin layer, it is preferable that 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 relative 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. That is, based on the total number of moles of aliphatic dicarboxylic acid units in all polyester resins contained in the resin composition, the content of succinic acid units in all polyester resins contained in the resin composition is preferably 40 mol% or more and 99 mol% or less, particularly preferably 50 mol% or more and 99 mol% or less, more preferably 50 mol% or more and 98 mol% or less, more preferably 60 mol% or more and 97 mol% or less, and particularly preferably 60 mol% or more and 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, particularly preferably 5 mol% or more, also preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 30 mol% or less.That is, based on the total number of moles of aliphatic dicarboxylic acid units in all polyester resins contained in the resin composition, 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.

[0024] When the content of succinic acid units and aliphatic dicarboxylic acid units having 9 to 36 carbon atoms satisfies the preferred ranges of (1) and / or (2) above, it becomes possible to obtain a resin composition that improves moldability and provides a resin layer that is superior in heat resistance, easy biodegradability, and surface slipperiness and smoothness.

[0025] One embodiment of the aliphatic polyester resin (A) according to the present invention is, for example, an aliphatic polyester resin (A) containing aliphatic diol units A1 represented by the following structural formula (1), succinic acid units A21 represented by the following structural formula (2), and aliphatic dicarboxylic acid units A22 represented by the following structural formula (3). The aliphatic polyester resin (A) according to this embodiment may contain two or more types of aliphatic diol units A1 represented by the following structural formula (1), or may contain two or more types of aliphatic dicarboxylic acid units A22 represented by the following structural formula (3), and may further contain structural units other than these structural units. -O-R １ -O- (1) -OC-CH ２ -CH ２ -CO- (2) -OC-R ２ -CO- (3)

[0026] In structural formula (1), R １ represents a divalent aliphatic hydrocarbon group which may have a substituent. ２is typically a substituted or unsubstituted divalent aliphatic hydrocarbon group having 7 to 34 carbon atoms, preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group having 7 to 11 carbon atoms. The aliphatic diol unit A1, aliphatic dicarboxylic acid unit A21, and aliphatic dicarboxylic acid unit A22 represented by the above structural formulas (1), (2), and (3) may be derived from compounds derived from petroleum or from compounds derived from plant materials, but are preferably derived from compounds derived from plant materials. Therefore, the bio-based carbon content of the aliphatic polyester resin (A) according to ISO 16620-2:2015 is preferably 10% or more, and 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 preferably 25% or more and 100% or less.

[0027] R １ and R ２ When the substituent and / or atom is substituted, the type of the substituent and / or atom is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include, independently of each other, 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.

[0028] The aliphatic diol that provides the diol unit A1 represented by the structural formula (1) is not particularly limited, but from the viewpoints 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 of these, 1,4-butanediol is particularly preferred. Two or more types of the aliphatic diols can also be used. The aliphatic dicarboxylic acid that provides 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, and brassylic acid. Among these, azelaic acid and sebacic acid are particularly preferred. Two or more of the above aliphatic dicarboxylic acids may be used. Specific examples of the aliphatic polyester-based resin (A) according to the present disclosure include those containing polybutylene succinate sebacate (PBSSe), which is 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.

[0029] (Other Copolymerizable Components) The aliphatic polyester resin (A) may contain 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 and strength and / or controlling biodegradability. When the aliphatic polyester resin (A) contains the other aliphatic dicarboxylic acid units A23 in addition to the succinic acid units A21 and the aliphatic dicarboxylic acid units A22 having 9 to 36 carbon atoms, 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%, based on 100 mol% of all dicarboxylic acid units in the aliphatic polyester resin (A). 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 %.

[0030] Examples of aliphatic dicarboxylic acids that provide the other aliphatic dicarboxylic acid units A23 include at least one aliphatic dicarboxylic acid selected from the group consisting of oxalic acid, malonic acid, and adipic acid. More specific examples of the aliphatic polyester resin (A) according to this embodiment that has the other aliphatic carboxylic acid units A23 include, for example, a resin in which the repeating structural unit A1 contains 1,4-butanediol units A11, and the content of 1,4-butanediol units A11 (A11 / A1) relative to the total number of moles of repeating structural units A1 in the aliphatic polyester resin (A) is 95 mol % or more and 100 mol % or less, and In contrast, an aliphatic polyester resin (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 relative to the total number of moles of the repeating structural unit A2 (A21 / A2) is 50 mol% or more and 89 mol% or less, and the content of the adipic acid unit A23 relative to the total number of moles of the repeating structural unit A2 (A23 / A2) is 0 mol% or more and less than 11 mol%. From the viewpoints of surface smoothness and biodegradation rate, 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, and there is no particular upper limit.

[0031] Further, other more specific examples of the aliphatic polyester-based resin (A) according to this embodiment having other aliphatic dicarboxylic acid units A23 include, for example, a resin 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-based resin (A) is 95 mol % or more and 100 mol % or less, and the content of the repeating structural units A2 relative to the total number of moles of the repeating structural units A2 is 95 mol % or more and 100 mol % or less. the content (A22 / A2) of the repeating structural unit A21 relative to the total number of moles of the repeating structural unit A2 is from 50 mol% to 89 mol%; the content (A23 / A2) of the adipic acid unit A23 relative to the total number of moles of the repeating structural unit A2 is from 0 mol% to 20 mol%, and the ratio ((A22 / A2) / (A23 / A2)) exceeds 1.

[0032] The aliphatic polyester resin (A) may further have a repeating structural unit (aliphatic oxycarboxylic acid unit) A3 derived from an aliphatic oxycarboxylic acid. Specific examples of the aliphatic oxycarboxylic acid component that provides the aliphatic oxycarboxylic acid unit A3 include 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, and 2-hydroxyisocaproic acid, as well as derivatives of these aliphatic oxycarboxylic acids, such as lower alkyl esters or intramolecular esters. When optical isomers exist, they may be in the D-form, L-form, or racemic form. 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 aliphatic oxycarboxylic acid component used as a raw material may be in the form of a solid, liquid, or aqueous solution.

[0033] When the polyester resin (A) contains these aliphatic hydroxycarboxylic acid units A3, the content thereof is, from the viewpoint of moldability, 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 structural units constituting the polyester resin (A) are taken as 100 mol%. That is, the content of the aliphatic hydroxycarboxylic acid units A3 is, based on the number of moles of all the structural units of the aliphatic polyester resin (A) (100 mol%), preferably 0 mol% or more and 20 mol% or less, particularly preferably 0 mol% or more and 10 mol% or less, more preferably 0 mol% or more and 5 mol% or less, and most preferably 0 mol% (not included, i.e., below the detection limit).

[0034] Furthermore, the aliphatic polyester resin (A) may contain, as dicarboxylic acid units other than the aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units such as furandicarboxylic acid, terephthalic acid, or isophthalic acid, as long as the effects of the present invention are not impaired.

[0035] The aliphatic polyester resin (A) may have an increased melt viscosity by copolymerizing a tri- or higher functional aliphatic polyhydric alcohol, a tri- or higher functional aliphatic polycarboxylic acid or an acid anhydride thereof, or a tri- or higher functional aliphatic polyoxycarboxylic acid component.

[0036] Specific examples of trifunctional aliphatic polyhydric alcohols include trimethylolpropane and glycerin, and specific examples of tetrafunctional aliphatic polyhydric alcohols include pentaerythritol. These may be used alone or in combination of two or more. Specific examples of trifunctional aliphatic polycarboxylic acids or acid anhydrides thereof include propanetricarboxylic acid or its acid anhydride, and specific examples of tetrafunctional polycarboxylic acids or its acid anhydrides include cyclopentanetetracarboxylic acid or its acid anhydride. These may be used alone or in combination of two or more.

[0037] 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, and either type can be used, but from the viewpoints of moldability, mechanical strength, and appearance of molded products, (i) a type having two carboxyl groups and one hydroxyl group in the same molecule, such as malic acid, is preferred, more specifically, malic acid is preferably used.Furthermore, tetrafunctional aliphatic oxycarboxylic acid components are divided into (i) a type having three carboxyl groups and one hydroxyl group in the same molecule, (ii) a type having two carboxyl groups and two hydroxyl groups in the same molecule, and (iii) a type having three hydroxyl groups and one carboxyl group in the same molecule, and either type can be used, but those having multiple carboxyl groups are preferred, more specifically, citric acid, tartaric acid, etc. These may be used alone or in combination of two or more.

[0038] When the aliphatic polyester resin (A) contains such a structural unit derived from a tri- or higher functional component, the content thereof, relative to all structural units constituting the polyester resin (A) as 100 mol %, is such that the lower limit is usually 0 mol % or more, preferably 0.01 mol % or more, and the upper limit is usually 5 mol % or less, preferably 2.5 mol % or less.

[0039] <Physical Properties of Aliphatic Polyester Resin (A)> (Weight Average Molecular Weight (Mw)) 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. However, because this is advantageous in terms of moldability and mechanical strength, it 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.

[0040] (Melt Flow Rate (MFR)) The melt flow rate (MFR) of the aliphatic polyester resin (A), as measured in accordance with JIS K7210-1:2014 at a temperature of 190°C and a load of 2.16 kgf, is usually 0.1 g / 10 min or more and 100 g / 10 min or less, 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. That is, the MFR measured in accordance with 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.

[0041] (Melting Point) 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 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. When there are multiple melting points, it is preferable that at least one of the melting points is within the above range.

[0042] The melting point of the aliphatic polyester resin (A) can be measured using a differential scanning calorimeter (for example, DSC8500 (manufactured by PerkinElmer Japan)). Specifically, about 5 mg of the aliphatic polyester resin (A) is precisely weighed, 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, and the melting point (peak top) can be measured.

[0043] (Method for producing aliphatic polyester resin (A)) The method for producing the aliphatic polyester resin (A) according to this embodiment can employ a known method for producing polyesters. Furthermore, the polycondensation reaction can be carried out under suitable conditions that have been conventionally employed, and is not particularly limited. Usually, a method is employed in which the degree of polymerization is further increased by carrying out a reduced pressure operation after the esterification reaction has proceeded.

[0044] When a diol component forming diol units (also referred to as "diol component providing diol units") and a dicarboxylic acid component forming dicarboxylic acid units (also referred to as "dicarboxylic acid providing dicarboxylic acid units") are reacted during the production of the aliphatic polyester resin (A), the amounts of the diol component and the dicarboxylic acid component used are set so that the aliphatic polyester resin (A) produced has the desired composition. Usually, the diol component and the dicarboxylic acid component react in substantially equimolar amounts, but the diol component is usually used in a 1 to 50 mol % excess over the dicarboxylic acid component because it is distilled off during the esterification reaction.

[0045] When the aliphatic polyester resin (A) contains components (optional components) other than the essential components such as polyfunctional component units, the corresponding compounds (monomers or oligomers) are reacted so that the polyfunctional component units also have the desired composition. In this case, there are no limitations on the timing and method of introducing the optional components into the reaction system, and they are arbitrary as long as the aliphatic polyester resin (A) suitable for the present invention can be produced.

[0046] The aliphatic polyester resin (A) is usually produced in the presence of a catalyst. As the catalyst, any catalyst that can be used in the production of known polyester resins can be selected as long as it does not significantly impair the effects of the present invention. Examples of the catalyst include metal compounds such as germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, and zinc. Among them, titanium compounds and germanium compounds are preferred.

[0047] Examples of titanium compounds that can be used as catalysts include 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.

[0048] In addition, other catalysts may be used in combination as long as the object of the present invention is not impaired. The catalysts may be used alone or in any combination and ratio of two or more.

[0049] 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, relative to the amount of monomer used. That is, 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. By setting the amount of catalyst used within the above range, the effects of using the catalyst can be reliably enjoyed, production costs can be reduced, and discoloration of the obtained polymer and a decrease in hydrolysis resistance can be prevented.

[0050] 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 the pressure reduction is started.

[0051] The reaction conditions, such as temperature, polymerization time, and pressure, when producing the aliphatic polyester resin (A) may be any as long as they do not significantly impair the effects of the present invention, but the reaction temperature for 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 higher, preferably 180° C. or higher, and an upper limit of usually 260° C. or lower, preferably 250° C. or lower. That is, the reaction temperature is preferably 150° C. or higher and 260° C. or lower, and particularly preferably 180° C. or higher and 250° C. or lower. By setting the reaction temperature within the above range, excessive generation of unsaturated bonds can be more reliably suppressed, gelation caused by unsaturated bonds can be prevented, and the polymerization reaction can be better controlled.

[0052] 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. That is, 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.

[0053] The polycondensation reaction after the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component is carried out under a pressure of usually 0.01×10 ３ Pa or more, preferably 0.03 × 10 ３ Pa or more, and the upper limit is usually 1.4 × 10 ３ Pa or less, preferably 0.4 × 10 ３ It is desirable to carry out the polycondensation reaction under a vacuum of 0.01×10 Pa or less. ３ Pa or more 1.4×10 ３ Pa or less is preferable, and 0.03 × 10 ３ Pa or more 0.4×10 ３ Pa or less is particularly preferred. The lower limit of the reaction temperature in the reaction is usually 150°C or more, preferably 180°C or more, and the upper limit is usually 260°C or less, preferably 250°C or less. That is, 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. When the reaction temperature is within the above range, excessive generation of unsaturated bonds can be more reliably suppressed, thereby preventing gelation caused by unsaturated bonds and enabling better control of the polymerization reaction.

[0054] Furthermore, the lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 10 hours or less. That is, the reaction time is preferably 2 hours or more and 15 hours or less, particularly preferably 2 hours or more and 10 hours or less.

[0055] <Resin composition (resin layer)> 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, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more. The upper limit is not particularly limited, and it is usually 100% by mass or less, and may be less than 100% by mass. That is, the content of the aliphatic polyester resin (A) in the resin composition (resin layer) is preferably 5% by mass or more and 100% 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, more preferably 20% by mass or more and 100% by mass or less, and even more preferably 25% by mass or more and 100% by mass or less, based on the mass of the resin composition or resin layer. The resin composition or resin layer may contain two or more aliphatic polyester resins (A). Specifically, for example, two or more aliphatic polyester resins (A) differing in the type or ratio of constituent units, production method, physical properties, etc. When the resin composition or resin layer contains two or more aliphatic polyester resins (A), the content of the aliphatic polyester resins (A) in the resin composition or resin layer refers to the content of all aliphatic polyester resins (A) in the resin composition or resin layer.

[0056] (Polyhydroxyalkanoate (C)) From the viewpoint of adjusting rigidity, heat resistance, and biodegradability, the resin composition or the resin layer may further contain a polyhydroxyalkanoate (C) different from the aliphatic polyester resin (A). 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.)

[0057] Specific examples of the polyhydroxyalkanoate (C) may include a homopolymer of one type of hydroxyalkanoate, a copolymer composed of two or more types of hydroxyalkanoates, or a copolymer composed of one or more types of hydroxyalkanoates and other monomers. Examples of the homopolymer include poly(3-hydroxybutyrate). Examples of the copolymer (copolymer resin) include poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resin, poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) copolymer resin, and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resin. From the viewpoint of moldability, 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 it 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. In particular, from the viewpoints of moldability and the physical properties of the resulting molded article, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin, i.e., PHBH, is preferred.

[0058] When the polyhydroxyalkanoate (C) has a structural unit C11 derived from 3-hydroxybutyrate, i.e., a 3-hydroxybutyrate unit C11, from the viewpoints of moldability and thermal stability, the polyhydroxyalkanoate (C) preferably contains 60 mol% or more of the 3-hydroxybutyrate unit C11, particularly preferably 70 mol% or more, and even more preferably 75 mol% or more, relative to 100 mol% of all structural units constituting the polyhydroxyalkanoate (C). The upper limit is not particularly limited, but is preferably 100 mol% or less, preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less. That is, the content of the 3-hydroxybutyrate unit C11, relative to all structural units of the 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 95 mol% or less. When the content is within the above range, crystallization is further promoted, which further improves molding productivity. In addition, molding temperature and thermal decomposition temperature can be prevented from becoming close to each other, which makes molding easier.

[0059] The ratio of each monomer in polyhydroxyalkanoate (C) can be measured by gas chromatography as follows. 2 ml of a sulfuric acid / methanol mixture (15 / 85 (mass ratio)) and 2 ml of chloroform are added to approximately 20 mg of dried PHA, 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 added little by little to neutralize the mixture, and the mixture is left to stand until the evolution of carbon dioxide gas stops. 4 ml of diisopropyl ether is added and mixed well, and 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 polyhydroxyalkanoate (C).

[0060] The weight average molecular weight (hereinafter sometimes referred to as Mw) of the polyhydroxyalkanoate (C) can be measured by the above-mentioned gel permeation chromatography (GPC), and the weight average molecular weight (Mw) using monodisperse polystyrene as the standard substance 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 and moldability of the resin layer.

[0061] The melt flow rate (MFR) of the polyhydroxyalkanoate (C) is preferably 1 g / 10 min or more and 100 g / 10 min or less, as measured at a temperature of 190°C and a load of 2.16 kg according to JIS K7210-1:2014. From the viewpoints 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 the polyhydroxyalkanoate (C) can be adjusted by the molecular weight. That is, the MFR of the 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.

[0062] The melting point of the 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 lower than 160° C. That is, the melting point of the 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 lower 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.

[0063] 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 depository authority: National Institute of Advanced Industrial Science and Technology International Patent Organism Depositary (6-1 Central, 1-1 Higashi, Tsukuba, 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)).

[0064] Furthermore, commercially available products can also be used as the polyhydroxyalkanoate (C), and examples of commercially available products of the polyhydroxyalkanoate (C) containing 3-hydroxybutyrate units and 3-hydroxyhexanoate units as 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.

[0065] The polyhydroxyalkanoate (C) may be used alone, or two or more polyhydroxyalkanoates (C) differing in the type of constituent unit, the ratio of constituent units, the production method, or physical properties may be blended and used.

[0066] (Aliphatic polyester resin (A) and polyhydroxyalkanoate (C) content ratio) When the resin composition (resin layer) contains polyhydroxyalkanoate (C), the mass ratio of the aliphatic polyester resin (A) and polyhydroxyalkanoate (C) contained in the resin composition (resin layer) is, from the viewpoint of improving rigidity and ease of molding processability, preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, particularly preferably 80 mass% or more, relative to the total mass of the aliphatic polyester resin (A) and the polyhydroxyalkanoate (C). Also, preferably less than 100 mass%, more preferably 99 mass% or less. That is, 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% 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 does not need to contain polyhydroxyalkanoate (C), that is, the content of the aliphatic polyester resin (A) may be 100% by mass.

[0067] (Other Resins) The resin composition may contain resins (other resins) other than the aliphatic polyester resin (A) and the optional polyhydroxyalkanoate (C) as long as the effects of the present invention are not impaired. Examples of other resins 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, biodegradable resins such as aliphatic aromatic polyesters such as PBAT, PBST, or PBSeT. One type of other resin may be used alone, or two or more types may be used in combination.

[0068] Specifically, for example, the resin composition (resin layer) may contain, as the other resin, 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). Such other resin 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 that 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 that 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. Here, 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). Specific examples of the 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).Furthermore, specific examples of the third aliphatic polyester resin (B3) include at least one resin selected from the group consisting of polylactic acid (PLA) and polycaprolactone (PCL). The content described in the above section "(2) Content of 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).

[0069] (Content ratio of aliphatic polyester resin (A), second aliphatic polyester resin (B1), aliphatic-aromatic polyester resin (B2), third aliphatic polyester resin (B3), and polyhydroxyalkanoate (C)) When 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 polyhydroxyalkanoate (C), the ratio of the mass of the aliphatic polyester resin (A) contained in the resin composition (resin layer) to the mass of the second aliphatic polyester resin (B1), the aliphatic-aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and polyhydroxyalkanoate (C) is 1 / 2. From the viewpoint of improving the rigidity of a molded article of the resin composition and facilitating molding processability of the molded article, the content of the aliphatic polyester resin (A) relative to the total mass of the aliphatic polyester resin (A) and the second aliphatic polyester resin (B1), the aliphatic-aromatic polyester resin (B2), the third aliphatic polyester resin (B3), and the polyhydroxyalkanoate (C) 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. Also, it is preferably less than 100% by mass, more preferably 99% by mass or less. That is, the content of the aliphatic polyester resin (A) ((A) / ((A)+(B1)+(B2)+(B3)+(C)) 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 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%. Furthermore, when 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), 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 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 95% by mass or less, and particularly preferably 90% by mass or less. The lower limit is 0% by mass, although the second aliphatic polyester resin (B1) is 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 all polyester resins in the resin composition [((B2) + (B3)) / ((A) + (B1) + (B2) + (B3) + (C)] is preferably 50% by mass or less, particularly preferably 40% by mass or less. The lower limit is 0% by 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% by mass, and particularly preferably 0 to 40% by mass. Furthermore, 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. Furthermore, since polyhydroxyalkanoate (C) is an optional component, the lower limit is 0% by mass. In other words, 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.

[0070] (Other Components) The resin composition may contain various additives such as inorganic fillers, lubricants, plasticizers, antistatic agents, antioxidants, light stabilizers, UV absorbers, dyes, pigments, hydrolysis inhibitors, crystal nucleating agents, antiblocking agents, light resistance agents, plasticizers, heat stabilizers, flame retardants, release agents, antifogging agents, surface wetting improvers, incineration aids, dispersing aids, various surfactants, or slip agents, as well as fine powders of animal or plant substances such as starch, cellulose, paper, wood flour, chitin / chitosan, coconut shell powder, or walnut shell powder, or mixtures thereof, as "other components." The resin composition may also contain functional additives such as freshness-preserving agents or antibacterial agents. These may be blended in any amount within the range that does not impair the effects of the present invention, and may be used alone or in combination of two or more.

[0071] In order not to impair the physical properties of the resin composition, the content of these other components is usually preferably such that the total amount of the other components is 0.01 mass % or more and 15 mass % or less relative to the total amount of the resin composition.

[0072] The alkali metal content in the resin composition is not particularly limited, but from the viewpoint of biodegradability and long-term storage stability, a low content is preferable. Specifically, it is preferably 50.0 ppm by mass or less, more preferably 30.0 ppm by mass or less, even more preferably 20.0 ppm by mass or less, particularly preferably 10.0 ppm by mass or less, and even more preferably 6.0 ppm by mass or less, and may even be 3.0 ppm by mass or less. More preferably, it is 0.0 ppm by mass (below the detection limit). The content can be reduced by purifying the raw materials. The alkali metal content can be measured using known methods such as high-frequency inductively coupled plasma atomic emission spectroscopy. 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. The upper limit is not particularly limited and 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, and particularly preferably 25% or more and 100% or less. Furthermore, the resin composition (resin layer) and the film for forming an inorganic vapor deposition film preferably have a half-crystallization time at a temperature of 50°C of 0.35 minutes or more, particularly preferably 0.38 minutes or more, and particularly preferably 0.40 minutes or more. The upper limit of the half-crystallization time is not particularly limited, but is preferably, for example, 10 minutes or less, particularly preferably 8 minutes or less. That is, the half-crystallization time of the resin composition (resin layer) and the film for forming an inorganic vapor deposition 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. By satisfying the above-mentioned half-crystallization time, it is possible to obtain the effect of more easily adjusting the wetting tension and / or surface roughness of the surface of the resin layer or the film for forming an inorganic vapor deposition film on which the inorganic vapor deposition film is formed. 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-deposited 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.The sample is then cooled at a rate of 100°C / min, and isothermal crystallization measurement is carried out at a temperature of 50°C, and the time required for crystallization to be half completed at a temperature of 50°C is calculated.

[0073] [Method for producing resin composition] The resin composition is produced by a method including a mixing step of mixing an aliphatic polyester resin (A), preferably further including 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.

[0074] This mixing step is carried out by mixing the aliphatic polyester resin (A), and the polyhydroxyalkanoate (C) that may be further contained, other resins, and other components in a predetermined ratio simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder, and preferably melt-kneading the mixture.

[0075] The kneader used in the mixing step may be a melt kneader. Although there is no limitation on the type of twin-screw extruder or single-screw extruder, 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.

[0076] The temperature during melt-kneading is preferably 120 to 220°C, and more preferably 130 to 180°C. This temperature range makes it possible to shorten the time required for melt-kneading, prevent deterioration in color tone due to resin degradation, and further improve practical physical properties such as impact resistance and moist heat resistance. Furthermore, from the viewpoint of further preventing the same resin degradation as described above, the melt-kneading time should not be unnecessarily long, and is preferably 20 seconds or more and 20 minutes or less, more preferably 30 seconds or more and 15 minutes or less, and it is preferable to set the time so as to satisfy these conditions together with the temperature.

[0077] [Forming of Resin Layer] The resin layer of the laminate or laminate film can be obtained by forming the resin composition into a film (film forming).

[0078] Examples of methods for forming the resin composition into a film include injection molding, extrusion molding, co-extrusion molding (film formation by inflation method or T-die method), lamination molding, heat press molding, blow molding (various blow moldings), thermoforming (vacuum forming, pressure forming), plastic processing, powder molding (rotational molding), etc. Among these, methods of forming by extrusion molding or inflation molding (inflation method) or the T-die method are particularly preferred because the effects of the present invention are significantly exhibited.

[0079] More specifically, for example, a method can be mentioned in which a film-like, sheet-like or cylindrical product extruded to a predetermined thickness from a T-die, I-die, round die or the like is cooled and solidified by a cooling roll, water, compressed air, etc. In this case, 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.

[0080] In the case of inflation molding, conditions such as bubble internal pressure, heating temperature, bubble diameter, cooling rate, and take-up speed can be conventionally used. For example, the tear strength of the film can be adjusted by adjusting the blow ratio, typically from 1.1 to 10 times, preferably from 2 to 5 times. In addition, the suitability for inflation molding can be determined visually by observing bubble stability or frost line height. For example, the more stable the bubble, the more preferable it is, and the more symmetrical the bubble shape. It is preferable that the frost line height is not too high. If the frost line is too high, the tubular film will not solidify easily, which can lead to film blocking and poor opening. If the frost line is too low, the bubble may come into contact with the air ring or die, preventing molding. Therefore, the frost line height must be adjusted to an appropriate height for the equipment, raw materials used, and processing conditions.

[0081] The resin temperature in the die is usually 100°C or higher so that the melt viscosity does not become too high and the extrusion rate per 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 in the die is preferably 110 to 250°C, more preferably in the range of 120 to 200°C.

[0082] The film obtained by such inflation molding may have a single layer structure or a laminated structure. The thickness of the film obtained by inflation molding, i.e., the film substrate, is usually 6 to 100 μm, preferably 10 to 50 μm.

[0083] In the case of T-die molding, 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 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, more preferably 130 to 220°C.

[0084] Furthermore, it is desirable to quickly cool the extruded molten resin to prevent blocking during winding, and it is usually desirable to cool it using an electrostatic contact type or touch roll type casting roll. In this case, the surface temperature of the casting roll is usually controlled to 15 to 70°C, preferably 20 to 60°C. Furthermore, when the sheet thickness is 1 mm or more, it is desirable to use a multistage cooling roll. Other commonly known molding conditions can be used.

[0085] The film obtained by T-die molding may have either a single layer structure or a laminate structure. The thickness of the film obtained by T-die molding, i.e., the film substrate, is usually 3 to 200 μm, and preferably 5 to 100 μm.

[0086] The film-like molded article obtained by the inflation method or T-die method may then be uniaxially or biaxially stretched by a roll method, a tenter method, a tubular method, or the like. When stretching, 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 both the longitudinal and transverse directions. After stretching, the film may be heat-treated by a method of blowing hot air, irradiating with infrared rays, irradiating with microwaves, or by contacting with a heat roll, or the like.

[0087] (Surface Slipperiness of Film) 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, as measured by the method specified in JIS K7125:1999. Furthermore, the dynamic friction coefficient, as measured by the method specified in JIS K7125:1999, is preferably 0.15 to 1.00, more preferably 0.17 to 0.90. When the static friction coefficient and the dynamic friction coefficient are within the above ranges, blocking between films during film formation or formation of the inorganic vapor deposition film can be more reliably prevented. Furthermore, the wetting tension of the resin layer and the inorganic vapor deposition film-forming surface of the film for forming an inorganic vapor deposition film can be more easily optimized, thereby further improving the adhesion between the resin layer and the inorganic vapor deposition film. As a method for adjusting the static friction coefficient and dynamic friction coefficient of the resin layer and the film for forming an inorganic vapor-deposited film to fall within the above ranges, for example, the content of aliphatic dicarboxylic acid units having 9 to 36 carbon atoms may be adjusted to fall within a predetermined range, thereby suppressing the bleed-out of low-molecular-weight components.

[0088] (Surface Smoothness of Resin Layer / Inorganic Vapor Deposited Film) The arithmetic mean height (arithmetic mean roughness) Ra of the roughness curve of at least one surface of the resin layer and the inorganic vapor deposition film (the surface on which the inorganic vapor deposition film is formed), measured by the method specified in JIS B0601:2001, is preferably 0.25 μm or less, and particularly preferably 0.20 μm or less. While there is no particular lower limit, from the viewpoint of more reliably preventing blocking between films, it is preferably 0.01 μm or more, and particularly preferably 0.05 μm or more. That is, the arithmetic mean height Ra is preferably 0.01 μm or more and 0.25 μm or less, and particularly preferably 0.05 μm or more and 0.20 μm or less. A specific method for adjusting the Ra of at least one surface of the resin layer and the inorganic vapor deposition film to fall within the above range includes, for example, adjusting the content of aliphatic dicarboxylic acid units having 9 to 36 carbon atoms to fall within a predetermined range. In measuring Ra, the scanning direction of the stylus on the measurement surface of the resin layer and the film for forming an inorganic vapor-deposited film may be either MD or TD. That is, it is preferable that Ra measured in at least one direction selected from the group consisting of MD and TD is within the above range. In measuring Ra, 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.

[0089] [Formation of inorganic vapor deposition film] 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.

[0090] 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 the viewpoint of economy. That is, the thickness of the inorganic vapor deposition film is preferably 20 to 100 nm, and particularly preferably 30 to 70 nm.

[0091] The inorganic substance used as the inorganic vapor deposition film is not particularly limited. For example, pure aluminum (99.9 mol% or more) can be used. However, other materials 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 are preferred. Materials containing 92 to 99.5 mol% aluminum and 0.5 to 8 mol% of the additive element are even more preferred. This is thought to be because, compared to pure aluminum, the crystals in the thin film layer are finer, which increases the path for permeating gas, improves the strength of the thin film, and makes it difficult for the additive particles forming the surface irregularities to fall off. When it is necessary to improve the gloss of the inorganic vapor deposition film, the amount of the additive element added is preferably 10 mol% or less, more preferably 7 mol% or less, and even more preferably 4 mol% or less.

[0092] In applications where transparency is particularly required for a laminate or film (laminated film), it is preferable to use a thin film made of the above-mentioned material (hereinafter referred to as "transparent vapor deposition material") that has been subjected to oxidation or oxynitridation treatment as the inorganic vapor deposition film. In the vapor deposition method, oxides or nitrides with low reaction orders are heated by irradiation with electron beams or the like in a high-vacuum chamber. At this time, a small amount of oxygen or nitrogen is appropriately introduced to control the reaction order. In the sputtering method, an alloy target is used, and the desired inorganic vapor deposition film can be formed by mixing an appropriate amount of nitrogen and / or oxygen with argon gas and depositing the film while reacting.

[0093] Examples of the transparent vapor deposition material include silicon oxide, aluminum oxide, aluminum alloy, a composite of silicon oxide and aluminum oxide, zinc oxide, and titanium oxide. From the viewpoint of ease of handling, the transparent vapor deposition material preferably 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 composite of silicon oxide and aluminum oxide (particularly, at least one inorganic substance selected from these). Silicon oxide, aluminum oxide, or silicon oxide-aluminum oxide is more preferred, and silicon oxide or aluminum oxide is even more preferred. The oxidation order of these materials, for example, silicon oxide, is preferably X = 1.0 to 1.9, more preferably X = 1.3 to 1.7, in SiOx. This oxidation order can be controlled by the oxygen purity of the material during vapor deposition, the amount of oxygen introduced, and the like. The oxidation order is measured by ESCA. If X is less than 1.0, the film becomes colored and transparency is impaired, which is undesirable. If X is greater than 1.9, the gas barrier properties become insufficient.

[0094] In the production of a film, in order to improve the adhesion between the inorganic vapor deposition film and the resin layer, it is preferable to perform an anchor coating before the film formation step, 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 vapor-depositing polyester films such as polyethylene terephthalate, but in consideration of environmental issues after biodegradation of the film substrate, it is preferable to use one or more types selected from the group consisting of polyester resins, polyurethane resins, polyacrylic resins, polyvinyl alcohol resins, polyolefin resins, and aliphatic polyester resins.

[0095] As the solvent for the anchor coat resin, alcohol-based solvents such as methyl alcohol, ethyl alcohol, and isopropanol, cyclohexane, dimethylformamide, ethyl acetate, water, benzene, toluene, acetone, tetrahydrofuran, dioxane, chloroform, and 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.

[0096] The thickness of the anchor coat layer formed by coating with such an anchor coat agent is preferably 0.01 to 5 μm, and more preferably 0.1 to 2 μm.

[0097] Furthermore, in order to further enhance the adhesion between the film substrate and the anchor coating layer, prior to the film formation step, the surface of the film substrate may be subjected to a corona treatment in a conventional manner, and at least one surface of the corona-treated resin layer may be coated with the anchor coating agent, preferably the corona-treated surface.

[0098] [Oxygen gas permeability of laminate or film (laminated film)] The oxygen gas permeability of the laminate or film (laminated film) is 10 cc / m ２ ・24hr·atm or less is preferable, 7cc / m ２ 24 hr·atm or less is more preferable, 4 cc / m ２ It is even more preferable that the oxygen gas permeability is 24 hr·atm or less. There is no particular restriction on the lower limit of the oxygen gas permeability, and a smaller value is preferable because it has better oxygen barrier properties. When the oxygen gas permeability of a laminate or film (laminated film) satisfies the above conditions, 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.

[0099] The oxygen gas permeability of the laminate or laminate film is measured by the method described in the Examples section below.

[0100] <Laminate> A laminate (hereinafter, sometimes simply referred to as "laminate") that 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) containing, 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.

[0101] The resin composition contained in the resin layer in the laminate may be the resin composition described above.

[0102] The vapor-deposited film in the laminate is preferably an inorganic vapor-deposited film, and the inorganic material formed on the film described above is preferably used as the inorganic vapor-deposited film. From the viewpoint of adhesion of the inorganic vapor-deposited film, the laminate is preferably a vapor-deposited film formed by vapor deposition on the surface of the resin layer. In this case, it is preferable to use the resin layer and inorganic vapor-deposited film described above for the film as the resin layer and inorganic vapor-deposited film, respectively.

[0103] The substrate layer is preferably a fiber or 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. Among these, from the viewpoint of making the resulting laminate biodegradable as a whole and forming an environmentally friendly packaging material, the substrate layer is preferably biodegradable. Specifically, the substrate layer preferably contains a plant-derived component, and more preferably is composed of a plant-derived component. Specific examples include paper, paperboard, pulp nonwoven fabric, cotton nonwoven fabric, rayon nonwoven fabric, polylactic acid film, and cellulose film, with paper, paperboard, polylactic acid film, and cellulose film being particularly preferred. Furthermore, composite films can also be used that are biodegradable by blending starch, chitosan, or the like with cellulose acetate or regenerated cellulose, which are not themselves biodegradable.

[0104] Examples of paper substrates include wrapping paper such as kraft paper or pure white roll paper; printing and information paper such as construction 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; and barrier paper provided 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 1,000 g / m ２ and particularly 30 to 700 g / m ２ It is preferable that:

[0105] One method for improving the dry strength of paper substrates is to internally add dry strength agents such as polyacrylamide, cationic starch, or amphoteric starch. The amount of dry strength agent added is typically 0.01 to 0.3% by mass based on the bone-dry pulp. Here, "internal addition" refers to adding an additive to the pulp slurry before papermaking. Another method involves increasing the beating degree of the pulp before papermaking to achieve a CSF of approximately 450 to 600 ml. Here, "CSF" refers to the Canadian Standard Freeness commonly used in the papermaking industry. Another method involves increasing the amount of softwood bleached kraft pulp (NBKP) added to the paper substrate.

[0106] Furthermore, because the paper substrate is hydrophilic, when the laminate comes into contact with water, water may penetrate from the edge of the laminate, causing the substrate layer to swell and become blistered or wrinkled, or the substrate layer may be broken down and peeled off. Therefore, for applications requiring water resistance, it is preferable to improve the sizing degree or wet strength of the paper substrate.

[0107] In paper substrates, methods for improving the sizing degree include the internal addition of an internal sizing agent such as alkyl ketene dimer. The amount of 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. Furthermore, methods for improving wet strength include the internal addition of an internal wet strength agent such as polyamide polyamine, polyamide polyamine epichlorohydrin modified product, or polyethylene imine epichlorohydrin modified product. The amount of internal wet strength agent added is usually 0.1 to 0.5% by mass based on the bone-dry pulp.

[0108] Paper or paperboard typically contains a filler known as a "filler." In order to improve the whiteness and opacity of the laminate, it is preferable to incorporate heavy calcium carbonate, titanium oxide, barium sulfate, or the like, either alone or in combination, into the substrate used. The amount of these fillers incorporated is typically 1 to 30% by mass relative to the paper substrate. Other fillers may be selected and used as needed, including inorganic fillers such as talc, kaolin, calcined kaolin, clay, diatomaceous earth, magnesium carbonate, aluminum hydroxide, magnesium sulfate, silica, aluminosilicates, and bentonite, as well as organic fillers such as polystyrene particles and urea-formaldehyde resin particles. To particularly increase the opacity of the laminate, graphite or carbon black may be incorporated into the substrate layer, or the surface of the substrate layer may be printed in black.

[0109] Nonwoven fabrics can also be used for the substrate layer. Specific examples include Bemliese (registered trademark) manufactured by Asahi Kasei Corporation, which is a hydroentangled nonwoven fabric made from cotton linters, Kinocloth (registered trademark) manufactured by Oji Kinocloth Co., Ltd., which is an airlaid nonwoven fabric made from pulp, Piros (registered trademark) manufactured by Omikenshi Co., Ltd., which is a spunlaced nonwoven fabric made from rayon, Kuraflex (registered trademark) manufactured by Kuraray Co., Ltd., which is a hydroentangled nonwoven fabric made from rayon, Terramac (registered trademark) manufactured by Unitika Ltd., which is a spunbonded nonwoven fabric made from polylactic acid, and Hibon (registered trademark) manufactured by Shinwa Co., Ltd.

[0110] 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., Materbee (registered trademark) manufactured by Novamont Co., Ltd., a blend film of starch and synthetic biodegradable polymer, Doron CC (trade name) manufactured by Aicello Chemical Co., Ltd., a blend film of chitosan, cellulose, and starch, Kuredux (registered trademark) manufactured by Kuraray Co., Ltd., a polyglycolic acid film, and Ecologe (registered trademark) manufactured by Mitsubishi Chemical Corporation, a PLA film, and the like.

[0111] When such a substrate layer is laminated and integrated onto the inorganic vapor deposition film side of the resin layer to produce a laminate, the substrate layer may be bonded to the inorganic vapor deposition film by, for example, a urethane adhesive, a polyester adhesive, etc. Alternatively, the bonding may be performed by extrusion lamination.

[0112] The laminate may be formed by laminating together a substrate layer, a vapor-deposited film, and a film substrate made of a resin composition, but may also have other layers as needed. The other layers are not particularly limited as long as they do not impair the objects of the present invention (gas barrier properties, thin film properties, etc.), and examples thereof include a printed layer, an adhesive layer, etc.

[0113] In the laminate, the mass proportion of the aliphatic polyester resin (A) relative to the total mass of the base layer and the resin layer is preferably 5 to 80 mass%, more preferably 10 to 70 mass%. If 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 if it is equal to or less than the upper limit of the above range, sufficient rigidity can be obtained.

[0114] The total thickness of the laminate is preferably 10 to 300 μm, particularly preferably about 20 to 250 μm, from the viewpoints of biodegradability, thin film properties, mechanical strength, processing stability, and the like.

[0115] [Water vapor transmission rate (moisture permeability) of laminate or film (laminated film)] The water vapor transmission rate (moisture permeability) of the laminate or film (laminated film) is 10 g / m ２ ・24 hours or less is preferable, 7 g / m ２ 24 hours or less is more preferable, 4 g / m ２ - 24 hours or less is more preferable. The lower limit of the water vapor transmission rate is not particularly limited, and a smaller value is preferable because it has better oxygen barrier properties. When the water vapor transmission rate (moisture permeability) of a 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%).

[0116] [Oxygen gas permeability of laminate or film (laminated film)] The oxygen gas permeability of the laminate or film (laminated film) is 10 cc / m ２ ・24hr·atm or less is preferable, 7cc / m ２ 24 hr·atm or less is more preferable, 4 cc / m ２ It is even more preferable that the oxygen gas permeability is 24 hr·atm or less. There is no particular restriction on the lower limit of the oxygen gas permeability, and a smaller value is preferable because it has better oxygen barrier properties. When the oxygen gas permeability of a laminate or film (laminated film) satisfies the above conditions, 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.

[0117] The oxygen gas permeability can be measured using an oxygen permeability measuring device under conditions of a temperature of 23°C and a humidity of 75% RH in accordance with JIS K7126-2: 2006. In the examples described below, an "OX-TRAN" (trade name, manufactured by MOCON Corporation, USA) was used as the oxygen permeability measuring device.

[0118] <Applications> The laminate and film (laminate 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. In addition, 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 for disposable applications. Specific preferred uses include, for example, agricultural mulch film, tunnel film, greenhouse film, sunshade, weed control sheet, ridge sheet, germination sheet, forestry fumigation sheet, binding tape containing flat yarn or the like, diaper back sheet, packaging sheet, shopping bag, plastic bag, garbage bag, draining bag, compost bag, oily food packaging, dried food packaging, processed livestock product packaging, processed seafood product packaging, beverage / liquid food packaging, dried confectionery packaging, snack food packaging, instant noodle packaging, retort food packaging, chilled / frozen food packaging, packaging for black tea, green tea, coffee, etc., packaging for supplements, packaging for cosmetics, packaging for electronic components, or packaging for optical components.

[0119] Another embodiment of the present invention is a packaging material having the above-mentioned film or laminate, and specific uses are as described above. Furthermore, as described above, by using an aliphatic polyester-based resin (A) in a film (laminated film) having a resin layer and an inorganic vapor-deposited film formed on at least one surface of the resin layer, it is possible to obtain a laminate film in which the resin layer and the inorganic vapor-deposited film have high adhesion and further improved biodegradability (home compostability, marine biodegradability). Similarly, by using an aliphatic polyester-based resin (A) in the resin layer of a laminate in which a substrate layer, a vapor-deposited film, and a resin layer are laminated in this order, it is possible to obtain a laminate in which the vapor-deposited film and the resin layer have high adhesion and further improved biodegradability (home compostability, marine biodegradability). Thus, the present invention also provides a new use of an aliphatic polyester-based resin (A) in a resin layer or film on which an inorganic vapor-deposited film is formed.

[0120] Specific embodiments of the present invention will be described in more detail below using examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. Note that the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limit values ​​in the embodiments of the present invention, and preferred ranges may be defined by a combination of the above-mentioned upper or lower limit values ​​and the values ​​in the following examples or values ​​between the examples.

[0121] <Raw Materials Used> The raw materials used in the Examples and Comparative Examples were polymerized resins or commercially available products as follows. In the following, "PBS" stands for "polybutylene succinate," "PBSA" stands for "polybutylene succinate / adipate," and "PHBH" stands for "poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)."

[0122] Preparation of Polycondensation Catalyst: 343.5 parts by weight of magnesium acetate tetrahydrate was placed in a reactor equipped with a stirrer, followed by 1,434 parts by weight of anhydrous ethanol (purity 99% by mass or higher). 218.3 parts by weight of ethyl acid phosphate (monoester:diester weight ratio 45:55) was then added, and the mixture was stirred at 23°C. After confirming that the magnesium acetate was completely dissolved, 410.0 parts by weight of tetra-n-butyl titanate was added. Stirring was continued for an additional 10 minutes, yielding a homogeneous mixed solution. This mixed solution was concentrated under reduced pressure while maintaining a temperature below 60°C. Approximately half of the ethanol added was distilled off, leaving a translucent, viscous liquid. 1,108 parts by weight of 1,4-butanediol was added, and the mixture was further concentrated under reduced pressure while maintaining a temperature below 80°C, yielding a catalyst solution with a titanium atom content of 3.5% by mass.

[0123] 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 the following raw materials: 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 catalyst solution. The molar ratio of succinic acid to sebacic acid was 89:11, and the proportion of the amount of 1,4-butanediol to the total amount of succinic acid and sebacic acid was 1.30.

[0124] While stirring the contents of the vessel, nitrogen gas was introduced into the vessel, and the system was immersed in a nitrogen atmosphere by vacuum replacement. Next, the raw materials were dissolved at 160°C. After confirming that the raw materials were completely dissolved and the temperature of the distillation section 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 at 230°C under normal pressure for 1 hour. Five minutes before the end of the esterification reaction, a catalyst solution was added. After the esterification reaction, the temperature was raised from 230°C to 250°C over 30 minutes, and at the same time, 0.07 x 10 ３ The pressure was reduced to a pressure of 100 Pa or less, and polymerization was continued while maintaining the heated and reduced pressure state. The polymerization was terminated when a predetermined viscosity was reached, thereby obtaining an aliphatic polyester resin A-1 (amount of succinic acid units based on the total amount of dicarboxylic acid units: 89 mol %, amount of sebacic acid units: 11 mol %, MFR: 5.0 g / 10 min, melting point: 102°C).

[0125] Aliphatic Polyester Resin A-2 Aliphatic polyester resin A-2 (amount of succinic acid units relative to total dicarboxylic acid units: 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 for 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.

[0126] Aliphatic Polyester Resin A-3 Aliphatic polyester resin A-3 (amount of succinic acid units in total dicarboxylic acid units: 95 mol%, amount of sebacic acid units: 5 mol%, MFR: 5.0 g / 10 min, melting point: 108°C) was produced in the same manner as in Production Example for 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 changed to 95:5.

[0127] <Commercially available resins> PBS: "BioPBS (registered trademark) FZ91PM" manufactured by PTTMCC Biochem (amount of succinic acid units in total 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 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)

[0128] <Evaluation of Properties> Evaluation of various physical properties and properties in the examples and comparative examples was carried out according to the following methods.

[0129] [Resin] (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 in accordance with JIS K7210-1:2014. The unit is g / 10 min.

[0130] [Film (single layer film, film for forming inorganic vapor-deposited film) / Laminate (laminated film)] (Evaluation 1: Inflation moldability) Tube stability during inflation film molding was evaluated according to the following criteria. Rank A: The tube was stable and moldability was good. Rank B: The tube was unstable, such as meandering, and moldability was problematic. (Evaluation 2: Slipperiness (dynamic friction coefficient, static friction coefficient)) Using the film, the static friction coefficient and dynamic friction coefficient in the MD direction between the inner surfaces of the inflation film were measured according to JIS K7125:1999. If the static friction coefficient or dynamic friction coefficient is too small, it can cause the film to collapse when wound.

[0131] (Evaluation 3: Surface smoothness (arithmetic mean height Ra)) The arithmetic mean height Ra of the inflation film in the MD direction was measured according to JIS B0601:2001. A smaller arithmetic mean roughness value is preferable because it indicates better surface smoothness. To measure the arithmetic mean height Ra, a surface roughness measuring instrument (product name: Surfcom 480A; manufactured by Tokyo Seimitsu Co., Ltd.) was used, and a stylus with a tip radius of 2 μm was used. The evaluation speed was 0.6 mm / min, the evaluation length was 5.0 mm, and the cutoff value was 0.8 mm.

[0132] (Evaluation 4: Low-Temperature Heat Sealability) The heat seal strength was determined based on the heat seal strength test (7.4) specified in JIS Z1707:2019. A flat portion of the resin layer with a film thickness of 30 μm was used as the test piece, cut into a length and width of 15 cm. One end of the test piece was heat-sealed with a heat sealer so that the resin layer was aligned, and then cut into a 15 mm wide strip. Heat sealing was performed using a single-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 using a Tensilon-type universal testing machine at a peel angle of 180° and a tensile speed of 300 mm / min, measuring the load (N / 15 mm) at which the sealed portion peeled or broke. The evaluation criteria were as follows: Rank A (Good): 10 N / 15 mm or more Rank B (Unacceptable): Less than 10 N / 15 mm

[0133] (Evaluation 5: Surface tension) One surface of the film was treated with 80 w min / m ２ After the corona treatment, a wettability check pen (trade name: Dyne Pen, manufactured by Corona Supplies) was inserted into the film by 10 cm. 2 After applying the above, it was observed whether the applied state was maintained after 2 seconds. The maximum value at which the applied state could be maintained after 2 seconds was recorded as the surface tension of the film surface to be evaluated. Note that the higher the surface tension value, the better the adhesion with the vapor-deposited film.

[0134] (Evaluation 6: Water Vapor Transmission Rate) Using the film, the water vapor transmission rate was measured by the cup method based on JIS Z0208: 1976. The measurement conditions were 40°C and 90% RH.

[0135] (Evaluation 7: Oxygen Gas Permeability) Using the film, the oxygen gas permeability was measured under conditions of a temperature of 23°C and a humidity of 75% RH using an oxygen permeability measuring device (trade name: OX-TRAN; manufactured by MOCON Corporation, USA) in accordance with JIS K7126-2:2006.

[0136] (Evaluation 8: Biodegradability test in soil at room temperature (home compostability)) After storing the film in soil (moisture content 30% by mass) collected from a farm in Mie Prefecture for 3 months at 28±2°C, the weight was measured and the biodegradability in soil at room temperature (home compostability) was evaluated according to the following criteria. The decomposition rate was calculated using the following formula: Decomposition rate (%) = 100 - (sample weight after 3 months / sample weight before test) x 100 Rank +++: Decomposition rate is 90% or more Rank ++: Decomposition rate is 30% or more but less than 90% Rank +: Decomposition rate is less than 30%

[0137] (Evaluation 9: Biodegradation test in seawater) After storing the sheet in seawater collected from Yokkaichi Port in Yokkaichi City, Mie Prefecture at 28±2°C for 3 months, weight measurements were carried out and biodegradability in seawater was evaluated according to the following criteria. The degree of decomposition was calculated using the following formula: Decomposition degree (%) = 100 - (sample weight after 3 months / sample weight before test) x 100 Rank +++: Decomposition degree is 50% or more Rank ++: Decomposition degree is 10% or more but less than 50% Rank +: Decomposition degree is less than 10%

[0138] (Evaluation 10: Bio-based carbon content) The bio-based carbon content of each polyester resin was evaluated according to ASTM D6866. Specifically, the composition was burned to capture carbon dioxide, which was then reduced with hydrogen and a catalyst to recover the carbon atoms in the composition as graphite. Next, the carbon isotope ratio was measured using an accelerator mass spectrometer. Carbon isotope ratios are present in the atmosphere at a certain rate. １４ Because carbon is present in biomass (bio-based carbon), the same proportion of carbon is present in biomass. １４ C is included. １４ Since C decreases with a half-life of 5730 years, carbon derived from fossil resources １４ Therefore, the standard amount of carbon in the modern atmosphere is １４ C ratio in the sample １４ The bio-based carbon content was determined by calculating the proportion of C.

[0139] (Evaluation 11: Half-crystallization time) A predetermined amount of a sample taken from the resin composition (resin layer) or the film for forming an inorganic vapor-deposited film was placed in an aluminum pan for DSC measurement, and heated and melted at 200°C for 5 minutes using a differential scanning calorimeter under a nitrogen atmosphere. Then, the sample was cooled at 100°C / min, and isothermal crystallization measurement was performed at a temperature of 50°C, and the time required for half of the crystallization to be completed at a temperature of 50°C was calculated. As the differential scanning calorimeter, "DSC8500" (trade name, manufactured by PerkinElmer Japan) was used.

[0140] Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-6 As raw materials for aliphatic polyester films (resin layer, film for forming inorganic vapor-deposited film), the raw materials shown in Table 1 were blended in the ratios shown in Table 1, extruded into strands 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 aliphatic polyester films with a thickness of 30 μm 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 films were subjected to the above-mentioned Evaluations 1 to 5 and Evaluations 8 to 11, and their physical properties and characteristics were measured and evaluated. Note that, for Comparative Examples 1-4 to 1-6, films could not be obtained by inflation molding, so the evaluations for Evaluations 2 to 5 and Evaluations 8 to 11 were not performed.

[0141] [Example 2-1] A 30 μm thick monolayer film was produced in the same manner as in Example 1-1. Subsequently, in order to enhance adhesion, the surface of the film coated with the anchor coating agent was subjected to a corona treatment immediately before being wound on a winder. Prior to vapor deposition, an anchor coating agent consisting of 1 part by mass of a copolymer polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.), 0.1 parts 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 to a film thickness of 0.2 μm after drying, and then dried at 60°C. The resulting aliphatic polyester film showed no wrinkles or other abnormalities.

[0142] Next, the anchor-coated surface of the resulting aliphatic polyester film was coated with a vacuum of 1×10 using an electron beam heating vacuum deposition machine (manufactured by Raybold). －４ Vapor deposition was carried out continuously under an atmosphere of 1000 kPa (300 psi) to form an aluminum vapor deposition film having a thickness of 60 nm and made of aluminum with a purity of 99.9 mol %, thereby obtaining a laminated film.

[0143] Next, a substrate made of a 20 μm thick cellulose film (product name: Hakusan Cellophane #300; manufactured by Rengo Co., Ltd.) was fixed via an adhesive layer onto the vapor-deposited 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.

[0144] (Evaluation 12: Measurement of Peel Strength) The peel strength (degree of adhesion) between the aliphatic polyester film and the vapor-deposited film of the obtained laminate was measured. A strip-shaped test piece measuring 150 mm in length and 15 mm in width was cut out from the flat portion of the laminate as a test piece. The aliphatic polyester film and the vapor-deposited film were then peeled off from one end of the test piece in the longitudinal direction toward the other end by a length of 50 mm. Next, using the test piece in which the aliphatic polyester film and the vapor-deposited film had been partially peeled off, the load when the vapor-deposited film was peeled off from the substrate at a peel angle of 180° and a tensile speed of 300 mm / min was measured using a Tensilon universal testing machine, and the value (gf / 15 mm) was recorded. The higher the peel strength value, the better the adhesion between the film and the vapor-deposited film.

[0145] Comparative 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 μm, produced in the same manner as in Comparative Example 1-3, was used as the single-layer film.

[0146] The evaluation results of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 are shown in Table 2. The evaluation results of Example 2-1 and Comparative Example 2-1 are shown in Table 3.

[0147]

[0148]

[0149]

[0150] The results in Tables 2 and 3 show that the laminates and films (laminate films) according to the present disclosure have a high degree of biodegradability at room temperature, excellent marine biodegradability, and extremely high biodegradability, while also achieving extremely low moisture permeability and oxygen gas permeability. Furthermore, the resin layer and inorganic vapor deposition film-forming 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), thereby demonstrating excellent adhesion to the vapor deposition film. Thus, by providing a vapor deposition film on at least one surface, the resin layer or inorganic vapor deposition film-forming film according to the present disclosure can achieve low moisture permeability and oxygen gas permeability even with a small layer structure, making it particularly suitable for use as packaging materials, particularly food packaging materials and pharmaceutical packaging materials.

Claims

1. A laminate having a base layer, a vapor-deposited film, and a resin layer in this order, the resin layer containing a first aliphatic polyester-based resin (A), the first aliphatic polyester-based resin (A) containing 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 containing 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.

2. The laminate according to claim 1, wherein the repeating structural unit A22 is a repeating structural unit derived from an aliphatic dicarboxylic acid having 9 to 13 carbon atoms.

3. The laminate according to claim 1, wherein the repeating structural unit A22 is a repeating structural unit derived from sebacic acid.

4. The laminate described in claim 1, wherein the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 in the first aliphatic polyester resin (A) is 1 mol % or more and 50 mol % or less.

5. The laminate according to claim 4, wherein the content (A22 / A2) is 5 mol % or more and 40 mol % or less.

6. The laminate according to claim 4, wherein the content (A22 / A2) is 7 mol % or more and 40 mol % or less.

7. The laminate according to claim 4, wherein the content (A22 / A2) is 10 mol % or more and 30 mol % or less.

8. The laminate according to claim 4, wherein the content (A22 / A2) is 11 mol % or more and 30 mol % or less.

9. The repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester resin (A) is 95 mol% or more and 100 mol% or less, the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol% or more and 30 mol% or less, the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol% or more and 89 mol% or less, the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol% or more and 20 mol% or less, and The laminate according to claim 1, wherein the content ratio (A22 / A2) / the content ratio (A23 / A2) is greater than 1.

10. The laminate of claim 1, wherein the repeating structural unit A1 comprises a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 is 95 mol % or more and 100 mol % or less, the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol % or more and 89 mol % or less, and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol % or more and less than 11 mol %.

11. The laminate of claim 1, wherein the first aliphatic polyester-based resin (A) comprises polybutylene succinate sebacate (PBSSe).

12. The laminate according to claim 1, wherein the first aliphatic polyester resin (A) is polybutylene succinate sebacate (PBSSe).

13. The laminate according to claim 1, wherein the content of the first aliphatic polyester resin (A) in the resin layer is 10% by mass or more and 100% by mass or less.

14. The resin layer further comprises 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), and the third aliphatic polyester resin (B3) is at least one resin selected from the group consisting of polylactic acid (PLA) and polycaprolactone (PCL), The laminate according to claim 1 , wherein the polyhydroxyalkanoate (C) is a resin different from the first aliphatic polyester resin (A).

15. The laminate according to claim 1, wherein the resin layer further comprises a polyhydroxyalkanoate (C), the polyhydroxyalkanoate (C) being different from the first aliphatic polyester resin (A).

16. The laminate according to claim 15, wherein the polyhydroxyalkanoate (C) contains a repeating structural unit C11 derived from 3-hydroxybutyrate, and the ratio of the number of moles of the repeating structural unit C11 to the total number of moles of structural units constituting the polyhydroxyalkanoate (C) is 70 mol % or more.

17. The laminate described in claim 15, wherein the content of the first aliphatic polyester resin (A) ((A) / ((A)+(C))) in the resin layer is 70 mass% or more and less than 100 mass% with respect to the total mass of the first aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).

18. The laminate according to claim 14, wherein the content of the second aliphatic polyester resin (B1) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [(B1) / ((A)+(B1)+(B2)+(B3)+(C))] is 95 mass% or less.

19. The laminate according to claim 14, wherein a total content of the aliphatic aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [((B2)+(B3)) / ((A)+(B1)+(B2)+(B3)+(C))] is 50 mass% or less.

20. A laminate as described in claim 1, wherein the ratio of the total number of moles of repeating structural units derived from succinic acid in all polyester-based resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester-based resins contained in the resin layer is 50 mol% or more and 99 mol% or less.

21. The laminate described in claim 1, wherein the ratio of the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all polyester-based resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester-based resins contained in the resin layer is 1 mol % or more and 50 mol % or less.

22. The laminate described in claim 1, wherein the content of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer is 5 mol % or more and 40 mol % or less relative to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer.

23. The laminate according to claim 1, wherein the resin layer has a bio-based carbon content of 25% or more and a crystallization half time at a temperature of 50° C. of 0.35 minutes or more.

24. The laminate according to claim 1, wherein the content of alkali metals in the resin layer is 6.0 ppm by mass or less.

25. The laminate of claim 1, wherein the substrate layer comprises a plant-derived component.

26. The laminate according to claim 1, wherein 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.

27. A film having a resin layer and a vapor-deposited film provided on at least one surface of the resin layer, wherein the resin layer contains a first aliphatic polyester-based resin (A), the first aliphatic polyester-based 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, and the repeating structural unit A2 contains 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.

28. The film according to claim 27, wherein the repeating structural unit A22 is a repeating structural unit derived from an aliphatic dicarboxylic acid having 9 to 13 carbon atoms.

29. The film of claim 27, wherein the repeating structural unit A22 is a repeating structural unit derived from sebacic acid.

30. The film described in claim 27, wherein the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 in the first aliphatic polyester resin (A) is 1 mol % or more and 50 mol % or less.

31. The film according to claim 30, wherein the content (A22 / A2) is 5 mol % or more and 40 mol % or less.

32. The film according to claim 30, wherein the content (A22 / A2) is 7 mol % or more and 40 mol % or less.

33. The film according to claim 30, wherein the content (A22 / A2) is 10 mol % or more and 30 mol % or less.

34. The film according to claim 30, wherein the content (A22 / A2) is 11 mol % or more and 30 mol % or less.

35. The repeating structural unit A1 includes a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 in the first aliphatic polyester resin (A) is 95 mol% or more and 100 mol% or less, the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol% or more and 30 mol% or less, the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol% or more and 89 mol% or less, the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol% or more and 20 mol% or less, and 28. The film of claim 27, wherein the ratio (A22 / A2) / the ratio (A23 / A2) is greater than 1.

36. The film according to claim 27, wherein the repeating structural unit A1 comprises a repeating structural unit A11 derived from 1,4-butanediol, the content of the repeating structural unit A11 (A11 / A1) relative to the number of moles of the repeating structural unit A1 is 95 mol % or more and 100 mol % or less, the content of the repeating structural unit A22 (A22 / A2) relative to the number of moles of the repeating structural unit A2 is 11 mol % or more and 30 mol % or less, the content of the repeating structural unit A21 (A21 / A2) relative to the number of moles of the repeating structural unit A2 is 50 mol % or more and 89 mol % or less, and the content of the repeating structural unit A23 derived from adipic acid (A23 / A2) relative to the number of moles of the repeating structural unit A2 is 0 mol % or more and less than 11 mol %.

37. The film of claim 27, wherein the first aliphatic polyester-based resin (A) comprises polybutylene succinate sebacate (PBSSe).

38. The film of claim 27, wherein the first aliphatic polyester resin (A) is polybutylene succinate sebacate (PBSSe).

39. The film described in claim 27, wherein the content of the first aliphatic polyester resin (A) in the resin layer is 10% by mass or more and 100% by mass or less.

40. The resin layer further comprises 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), and the third aliphatic polyester resin (B3) is at least one resin selected from the group consisting of polylactic acid (PLA) and polycaprolactone (PCL), The film according to claim 27 , wherein the polyhydroxyalkanoate (C) is a resin different from the first aliphatic polyester resin (A).

41. The film of claim 27, wherein the resin layer further comprises a polyhydroxyalkanoate (C), the polyhydroxyalkanoate (C) being different from the first aliphatic polyester-based resin (A).

42. The film according to claim 41, wherein the polyhydroxyalkanoate (C) contains a repeating structural unit C11 derived from 3-hydroxybutyrate, and the ratio of the number of moles of the repeating structural unit C11 to the total number of moles of structural units constituting the polyhydroxyalkanoate (B) is 70 mol % or more.

43. The film described in claim 41, wherein the content of the first aliphatic polyester resin (A) in the resin layer ((A) / ((A)+(C))) is 70 mass% or more and less than 100 mass% relative to the total mass of the first aliphatic polyester resin (A) and the polyhydroxyalkanoate (C).

44. The film according to claim 40, wherein the content of the second aliphatic polyester resin (B1) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [(B1) / ((A)+(B1)+(B2)+(B3)+(C)] is 95 mass% or less.

45. The film according to claim 40, wherein a total content of the aliphatic-aromatic polyester resin (B2) and the third aliphatic polyester resin (B3) relative to the sum of the mass of the first aliphatic polyester resin (A) in the resin layer 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) [((B2)+(B3)) / ((A)+(B1)+(B2)+(B3)+(C))] is 50 mass% or less.

46. ​​The film described in claim 27, wherein the ratio of the total number of moles of repeating structural units derived from succinic acid in all polyester-based resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester-based resins contained in the resin layer is 50 mol% or more and 99 mol% or less.

47. The film described in claim 27, wherein the ratio of the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all polyester resins contained in the resin layer to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all polyester resins contained in the resin layer is 1 mol % or more and 50 mol % or less.

48. The film described in claim 27, wherein the content of repeating structural units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms in all of the polyester resins contained in the resin layer is 5 mol % or more and 40 mol % or less relative to the total number of moles of repeating structural units derived from aliphatic dicarboxylic acids in all of the polyester resins contained in the resin layer.

49. The film according to claim 27, wherein the content of alkali metals in the resin layer is 6.0 ppm by mass or less.

50. The film according to claim 27, wherein 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 composite of silicon oxide and aluminum oxide.

51. 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 formation step of forming an inorganic vapor deposition film on at least one surface of the resin layer, wherein the resin layer comprises a first aliphatic polyester resin (A) containing 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 units A2 include 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.

52. A method for producing a film as described in claim 51, comprising, prior to the film formation step, a corona treatment step of corona-treating the surface of the resin layer on which the inorganic vapor deposition film is to be formed, and a coating step of coating the surface that has been subjected to the corona treatment step with an anchor coating agent.

53. A film for forming an inorganic vapor deposition film comprising a first aliphatic polyester resin (A), wherein the first aliphatic polyester resin (A) 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, and 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 of 0.35 minutes or more.

54. A film for forming an inorganic vapor deposition film as described in claim 53, wherein the arithmetic mean height (arithmetic mean roughness) Ra of a roughness curve measured in at least one of the MD and TD directions on at least one surface of the film, based on Japanese Industrial Standards (JIS) B0601:2001, is 0.25 μm or less.

55. Use of a first aliphatic polyester-based resin (A) in a resin layer for improving the biodegradability of a film having a resin layer and an inorganic vapor-deposited film provided on at least one surface of the resin layer, 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, 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.

56. Use of a first aliphatic polyester-based resin (A) in a resin layer to improve the 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.

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