Molded film or molded sheet

Abstract

The present invention addresses the problem of providing a molded film or molded sheet that has exceptional tear resistance and / or impact resistance. The present invention provides a molded film or sheet obtained by molding a thermoplastic resin composition containing specific amounts of a thermoplastic resin (A) and crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of at least 50%. The thermoplastic resin composition has an Elmendorf tear strength of at least 3 N / mm or a puncture impact strength of at least 0.3 J.

Description

Film or sheet molding

[0001] The present invention relates to a film molded article or a sheet molded article.

[0002] Plastic waste is a burden on the global environment, affecting ecosystems, emitting harmful gases when burned, and contributing to global warming due to the large amount of heat generated by combustion. Biodegradable plastics are being actively developed as a material that can solve these problems.

[0003] Patent Document 1 describes a biodegradable and environmentally friendly thermoplastic resin composition that is obtained by blending 0.1 to 20 parts by weight of poly(3-hydroxyalkanoate) particles having an average particle size of 300 μm or less with 100 parts by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).

[0004] Japanese Patent Application Publication No. 2004-161802

[0005] However, the above-mentioned conventional techniques are not sufficient from the viewpoint of tear resistance and impact resistance of molded articles of thermoplastic resin compositions, and there is room for further improvement.

[0006] One embodiment of the present invention has been made in consideration of the above-mentioned current situation, and its object is to provide a film or sheet molded article that is excellent in at least one of tear resistance and impact resistance.

[0007] As a result of extensive research into solving the above problems, the present inventors have completed one embodiment of the present invention.

[0008] A film or sheet molding according to one embodiment of the present invention is a film or sheet molding obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (where the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), the thermoplastic resin composition satisfying one or more of the following (A) to (C): (A) having an Elmendorf tear strength of 3 N / mm or more as measured by the methods shown in (A1) to (A4) below: (A1) forming the thermoplastic resin composition into a film having a thickness of 40 μm to obtain a film molding; (A2) curing the film molding obtained in (A1) for 7 days under conditions of 23°C and 50% RH; (A3) measuring the film molding after curing according to JIS (A4) The tear strength (unit: N) is measured by a method in accordance with JIS K7128-2; (A3) The tear strength measured in (A4) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (B) The Elmendorf tear strength measured by the methods shown in (B1) to (B4) below is 3 N / mm or more: (B1) The thermoplastic resin composition is molded into a film having a thickness of 50 μm to 100 μm to obtain a film molded body; (B2) The film molded body obtained in (B1) is aged for 7 days under conditions of 23°C and 50% RH; (B3) The tear strength (unit: N) of the aged film molded body is measured by a method in accordance with JIS K7128-2; (B4) The tear strength measured in (B3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (C) The thermoplastic resin composition has an Elmendorf tear strength of 5 N / mm or more as measured by the following methods (C1) to (C4): (C1) The thermoplastic resin composition is molded into a film having a thickness of more than 100 μm and not more than 120 μm to obtain a film molded body; (C2) The film molded body obtained in (C1) is aged for 7 days under conditions of 23°C and 50% RH;(C3) The tear strength (unit: N) of the film molded article after aging is measured by a method in accordance with JIS K7128-2; (C4) The tear strength measured in (C3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength;

[0009] According to another embodiment of the present invention, there is provided a film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (wherein the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), and the thermoplastic resin composition has an impact energy of 0.3 J or more at the maximum impact force point in a puncture impact test measured by the following methods (1) to (3): (1) The thermoplastic resin composition is molded into a sheet having a thickness of 900 μm to obtain a sheet molded product; (2) The sheet molded product obtained in step (1) is aged for 7 days under conditions of 23° C. and 50% RH, and then cut out into a shape of 60 mm×60 mm; (3) The cut-out sheet molded product is subjected to ASTM The impact energy (J) at the maximum impact force point is measured using a method in accordance with D3763-15 at a test temperature of 23°C and a test speed of 3 m / sec.

[0010] According to one embodiment of the present invention, it is possible to provide a film or sheet molded article that is excellent in at least one of tear resistance and impact resistance.

[0011] An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the respective configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic literature and patent documents described in this specification are incorporated herein by reference. Furthermore, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)."

[0012] [1. Film Molded Product or Sheet Molded Product] A film molded product or sheet molded product according to one embodiment of the present invention is a film molded product or sheet molded product obtained by molding a thermoplastic resin composition, wherein the thermoplastic resin composition comprises 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (where the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), and the thermoplastic resin composition satisfies any one or more of the following (A) to (C): (A) an Elmendorf tear strength measured by the methods shown in (A1) to (A4) below is 3 N / mm or more; (A1) the thermoplastic resin composition is molded into a film having a thickness of 40 μm to obtain a film molded product; (A2) the film molded product obtained in (A1) is aged for 7 days under conditions of 23°C and 50% RH; (A3) The tear strength (unit: N) of the film molded body after aging is measured using a method in accordance with JIS K7128-2; (A4) The tear strength measured in (A3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (B) The Elmendorf tear strength measured using the methods shown in (B1) to (B4) below is 3 N / mm or more: (B1) The thermoplastic resin composition is molded into a film having a thickness of 50 μm to 100 μm to obtain a film molded body; (B2) The film molded body obtained in (B1) is aged for 7 days under conditions of 23°C and 50% RH; (B3) The tear strength (unit: N) of the film molded body after aging is measured using a method in accordance with JIS K7128-2; (B4) The tear strength measured in (B3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength; (C) The Elmendorf tear strength measured by the methods shown in (C1) to (C4) below is 5 N / mm or more: (C1) The thermoplastic resin composition is molded into a film having a thickness of more than 100 μm and not more than 120 μm to obtain a film molded article;(C2) The film molded body obtained in (C1) is aged for 7 days under conditions of 23°C and 50% RH; (C3) The tear strength (unit: N) of the film molded body after aging is measured using a method in accordance with JIS K7128-2; (C4) The tear strength measured in (C3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength;

[0013] According to another embodiment of the present invention, there is provided a film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (wherein the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), and the thermoplastic resin composition has an impact energy of 0.3 J or more at the maximum impact force point in a puncture impact test measured by the following methods (1) to (3): (1) The thermoplastic resin composition is molded into a sheet having a thickness of 900 μm to obtain a sheet molded product; (2) The sheet molded product obtained in step (1) is aged for 7 days under conditions of 23° C. and 50% RH, and then cut out into a shape of 60 mm×60 mm; (3) The cut-out sheet molded product is subjected to ASTM The impact energy (J) at the maximum impact force point is measured using a method in accordance with D3763-15 at a test temperature of 23°C and a test speed of 3 m / sec.

[0014] In this specification, the term "film molded product" refers to a product conforming to JIS20108:2012, specifically a thin film having a thickness of less than 0.25 mm. In this specification, the term "sheet molded product" refers to a product conforming to JIS20108:2012, specifically a thin plate having a thickness of 0.25 mm or more.

[0015] In this specification, "a film molded body or sheet molded body according to one embodiment of the present invention" may be referred to as "the present film molded body or the present sheet molded body." The present film molded body or the present sheet molded body is formed by molding a thermoplastic resin composition. In other words, the present film molded body or the present sheet molded body also comprises a thermoplastic resin composition. The thermoplastic resin composition contained in the present film molded body or the present sheet molded body may also be referred to as a thermoplastic resin composition according to one embodiment of the present invention. In this specification, "a thermoplastic resin composition according to one embodiment of the present invention" may also be referred to as "the present resin composition." The crosslinked resin particles (B) contained in the present resin composition may also be referred to as the crosslinked resin particles (B) according to one embodiment of the present invention. In this specification, "crosslinked resin particles (B) according to one embodiment of the present invention" may also be referred to as "the present crosslinked resin particles (B)." Furthermore, in this specification, "impact energy at the maximum impact force point in a puncture impact test" may also be referred to as "puncture impact strength."

[0016] The present film molded article or the present sheet molded article has the advantage of being excellent in at least one of tear resistance and impact resistance.

[0017] In a preferred embodiment of the present invention, the film or sheet molded article has a tensile impact strength (kJ / m ２ The film and sheet moldings also have the advantage of being excellent in tensile impact strength (kJ / m ２ The method for measuring the above will be described in detail in the Examples below.

[0018] The polyhydroxyalkanoate resin contained in the present crosslinked resin particles (B) is a biodegradable resin. Therefore, the present crosslinked resin particles (B) can be biodegradable. The present film molded product or the present sheet molded product is advantageous in terms of biodegradability because it contains the biodegradable crosslinked resin particles (B).

[0019] <Thermoplastic Resin Composition> The present resin composition contains 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) (where the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight).

[0020] The present film molded article or the present sheet molded article has the advantage of being excellent in at least one of tear resistance and impact resistance by containing the present resin composition.

[0021] First, the crosslinked resin particles (B) will be described.

[0022] <Crosslinked Resin Particles (B)> The crosslinked resin particles (B), i.e., the present crosslinked resin particles (B), contain a polyhydroxyalkanoate resin and have a gel fraction of 50% or more. In this specification, "polyhydroxyalkanoate resin" may be referred to as "PHA." The present film molding or the present sheet molding has the advantage of being excellent in at least one of tear resistance and impact resistance by containing the present crosslinked resin particles (B). In other words, the present crosslinked resin particles (B) can be used as a modifier for the thermoplastic resin (A), or as a tear resistance improver and impact resistance improver.

[0023] (PHA) "PHA" is a general term for polymers containing hydroxyalkanoic acid as a monomer unit (monomer repeating unit), and is generally biodegradable. PHA is an aliphatic polyester, preferably a polyester not containing an aromatic ring. In this specification, "PHA" refers to a polymer containing hydroxyalkanoic acid repeating units in an amount of 50 mol% or more of all monomer repeating units (100 mol%). PHA preferably contains hydroxyalkanoic acid repeating units in an amount of 60 mol% or more, more preferably 70 mol% or more, of all monomer repeating units (100 mol%).

[0024] The PHA is not particularly limited. Examples of PHA include polyglycolic acid, poly(3-hydroxyalkanoate)-based resin (hereinafter sometimes referred to as "P3HA"), and poly(4-hydroxyalkanoate)-based resin. One type of PHA may be used alone, or two or more types may be used in combination. The PHA preferably contains a poly(3-hydroxyalkanoate)-based resin, and more preferably is a poly(3-hydroxyalkanoate)-based resin (in other words, composed solely of a poly(3-hydroxyalkanoate)-based resin).

[0025] In this specification, "polyglycolic acid" refers to a group of all monomer repeating units (100 mol%) containing [—CH ２ The term "polyglycolic acid" refers to a resin containing 50 mol % or more of repeating units represented by the formula [—CH—CO—O—]. ２ The repeating units represented by the formula [—CO—O—] may account for 60 mol % or more, 70 mol % or more, 80 mol % or more, or 90 mol % or more of all the monomer repeating units (100 mol %).

[0026] The polyglycolic acid may be a homopolymer of glycolic acid, or a copolymer of glycolic acid and a monomer other than glycolic acid (for example, a copolymer of glycolic acid and lactic acid, or a copolymer of glycolic acid and caprolactone).

[0027] Polyglycolic acid can be obtained by known methods such as condensation polymerization of glycolic acid and ring-opening polymerization of glycolide.

[0028] The P3HA has the formula: [—CHR—CH ２ 3-hydroxyalkanoic acid repeating units represented by the formula: —CO—O— (wherein R is C ｎ H ２ｎ＋１ where n is an integer of 1 or more and 15 or less.) is a polyhydroxyalkanoate containing the 3-hydroxyalkanoic acid repeating unit as an essential repeating unit. In this specification, "P3HA" refers to a resin containing 50 mol % or more of the 3-hydroxyalkanoic acid repeating units out of all monomer repeating units (100 mol %). The P3HA preferably contains 60 mol % or more, and more preferably 70 mol % or more, of all monomer repeating units (100 mol %).

[0029] P3HA is not particularly limited and may be a homopolymer containing the repeating unit described above, or a copolymer containing the repeating unit described above. Examples of the copolymer include copolymers of 3-hydroxybutanoic acid (hereinafter sometimes referred to as "3HB") and one or more monomers selected from the group consisting of 3-hydroxypropionic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, and 3-hydroxyoctadecanoic acid. Alternatively, another example of the copolymer may be a copolymer of 3HB and one or more monomers selected from the group consisting of 4-hydroxybutanoic acid, 4-hydroxypentanoic acid, 4-hydroxyhexanoic acid, 4-hydroxyheptanoic acid, 4-hydroxyoctanoic acid, 4-hydroxynonanoic acid, 4-hydroxydecanoic acid, 4-hydroxyundecanoic acid, 4-hydroxydodecanoic acid, 4-hydroxytridecanoic acid, 4-hydroxytetradecanoic acid, 4-hydroxyhexadecanoic acid, and 4-hydroxyoctadecanoic acid.

[0030] Examples of P3HA include poly(3-hydroxybutyrate) (hereinafter sometimes referred to as "P3HB"), which is a homopolymer of 3HB, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as "P3HB3HH"), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (hereinafter sometimes referred to as "P3HB4HB"). Only one type of P3HA may be used, or two or more types may be used in combination. As used herein, "poly(X-co-Y)" refers to a copolymer containing X repeating units and Y repeating units, and is intended to mean a copolymer obtained by copolymerizing a monomer from which the X repeating unit is derived and a monomer from which the Y repeating unit is derived. Furthermore, during the production of P3HA by microorganisms, a small amount (less than 1 mol%) of a monomer may be copolymerized. However, if this does not significantly affect the physical properties of the resulting P3HA, the monomer is considered to be uncopolymerized, and the product will be referred to by a name that does not include that monomer.

[0031] P3HA can be produced by microorganisms. Such microbially produced P3HA is typically composed solely of D-form (R-form) 3-hydroxyalkanoic acid repeating units. Among microbially produced P3HAs, P3HB, P3HB3HH, and P3HB4HB are preferred, with P3HB3HH and P3HB4HB being more preferred, due to ease of industrial production.

[0032] It is also preferred that P3HA contains 3-hydroxybutanoic acid (3HB) repeating units. When P3HA contains 3HB repeating units, from the viewpoint of the balance between flexibility and strength, the composition ratio of 3HB repeating units in all monomer repeating units (100 mol%) is preferably 60 mol% to 99 mol%, more preferably 61 mol% to 97 mol%, and even more preferably 62 mol% to 95 mol%. When the composition ratio of 3HB repeating units in P3HA is 60 mol% or more, there is an advantage that the rigidity of the crosslinked resin particles (B) can be further improved. On the other hand, when the composition ratio of 3HB repeating units in P3HA is 99 mol% or less, there is an advantage that the flexibility of the crosslinked resin particles (B) tends to be further improved. The monomer composition ratio of P3HA can be measured by gas chromatography or the like (see, for example, WO 2014 / 020838). As P3HA, two or more types having different composition ratios of 3HB repeating units may be used in combination.

[0033] The microorganism that produces P3HA is not particularly limited as long as it has the ability to produce P3HA. For example, the first P3HB-producing bacterium was Bacillus megaterium, discovered in 1925, and other naturally occurring microorganisms such as Cupriavidus necator (formerly classified as Alcaligenes eutrophus and Ralstonia eutropha) and Alcaligenes latus are known. In these microorganisms, P3HB accumulates intracellularly.

[0034] Known examples of bacteria that produce copolymers of 3HB and other hydroxyalkanoic acids include Aeromonas caviae, which produces P3HB3HH, and Alcaligenes eutrophus, which produces poly(3-hydroxybutyrate-co-4-hydroxybutyrate). In particular, Alcaligenes eutrophus AC32 (FERM BP-6038) (T. Fukui, Y. Doi, J. Bacteriol., 179, pp. 4821-4830 (1997)), into which genes encoding P3HA synthases have been introduced, is preferred for increasing P3HB3HH productivity. Microbial cells obtained by culturing such microorganisms under appropriate conditions and allowing P3HA to accumulate within the cells are used. In addition to the above, genetically modified microorganisms into which various P3HA synthesis-related genes have been introduced may be used depending on the P3HA to be produced, or culture conditions, including the type of substrate, may be optimized.

[0035] The weight-average molecular weight of the PHA is not particularly limited. The weight-average molecular weight of the PHA is preferably 50,000 to 3,000,000, preferably 100,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When the weight-average molecular weight of the PHA is 50,000 or more, it has the advantage of being able to reduce or avoid the tendency for the crosslinked resin particles (B) to have a low strength. Also / alternatively, when the weight-average molecular weight of the PHA is 50,000 or more, it has the advantage of being able to reduce or avoid the tendency for the PHA to become sticky due to low molecular weight components. On the other hand, a PHA having a weight-average molecular weight of 3,000,000 or less may have the advantage of being easy to manufacture and / or easy to handle in order to achieve the object of one embodiment of the present invention. The numerical value of the weight-average molecular weight of the PHA is a value obtained by measuring the PHA before crosslinking treatment.

[0036] The weight-average molecular weight can be measured using gel permeation chromatography (GPC) (Shimadzu Corporation's "High Performance Liquid Chromatograph 20A System"), a polystyrene gel column (Showa Denko K.K.'s "K-G 4A" or "K-806M" or the like), and chloroform as the mobile phase. The weight-average molecular weight can be determined as a polystyrene-equivalent molecular weight using a calibration curve obtained by measuring polystyrenes with known molecular weights using the same measurement method. In this case, the calibration curve can be prepared using polystyrenes with weight-average molecular weights of 31,400, 197,000, 668,000, and 1,920,000. As the column for the GPC, a column appropriate for measuring the molecular weight can be used.

[0037] (Gel Fraction) In this specification, the term "crosslinked resin particles" refers to particles having a crosslinked structure in which molecular chains of the resin constituting the resin particles are bonded intramolecularly and / or intermolecularly. That is, the present crosslinked resin particles (B) may have a crosslinked structure in which molecular chains of PHA are bonded together. The amount of crosslinked structures in the crosslinked resin particles (B) affects the gel fraction of the crosslinked resin particles (B); specifically, the more crosslinked structures there are, the higher the gel fraction. The present crosslinked resin particles (B) have a certain amount or more of crosslinked structures, and therefore exhibit a high gel fraction, specifically a gel fraction of 50% or more. When the present crosslinked resin particles (B) have a gel fraction of 50% or more, the crosslinked resin particles (B) have excellent hardness, heat resistance, and solvent resistance.

[0038] The gel fraction value is preferably 60% or more, more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more. It may also be 85% or more, or 90% or more. The upper limit of the gel fraction is not particularly limited, as long as it is 100% or less. From the viewpoint of production efficiency of the crosslinked resin particles (B), the upper limit of the gel fraction is preferably 99.5% or less, more preferably 99% or less. The upper limit of the gel fraction may also be 98% or less, 97% or less, or 96% or less.

[0039] The gel fraction is a value measured as follows: (1) A dried product of crosslinked resin particles (B) is added to chloroform so that the concentration becomes 0.7% by weight, and the resulting mixture is maintained at 60°C for 30 minutes to obtain a chloroform solution; (2) The chloroform solution is then allowed to stand at room temperature for 3 hours, and the chloroform solution is then filtered through a membrane filter having a pore size of 0.45 µm; (3) The gel remaining on the filter is dried, and the weight of the dried gel together with the filter is measured, and the gel fraction is calculated using the following formula: Gel fraction (%) = {(Weight of filter including dried gel - Weight of filter only) / Weight of dried product of crosslinked resin particles (B) used for measurement} x 100.

[0040] (Volume average particle diameter) The volume average particle diameter of the present crosslinked resin particles (B) is preferably 0.10 μm to 10.00 μm. This configuration allows the crosslinked resin particles (B) to be suitably used in various applications as described below. From the viewpoint of practical use opportunities, the lower limit of the volume average particle diameter is more preferably 0.15 μm or more, and even more preferably 0.20 μm or more. Furthermore, from the viewpoint of productivity (such as PHA production and / or crosslinking treatment), the upper limit of the volume average particle diameter is more preferably 8.00 μm or less, and even more preferably 5.00 μm or less.

[0041] In this specification, the volume average particle diameter (MV) of the crosslinked resin particles is a value obtained by measuring an aqueous dispersion in which the crosslinked resin particles are dispersed in an aqueous medium. More specifically, the volume average particle diameter (MV) of the crosslinked resin particles is a value calculated by the following formula (1), i.e., formula (2), when the particle diameters of the individual crosslinked resin particles contained in a population of k crosslinked resin particles in total are denoted as d1, d2, ..., di... dk in ascending order, and the volumes of these individual crosslinked resin particles are denoted as V1, V2, ..., Vi... Vk (where Vi is the volume of the crosslinked resin particle with particle diameter di):

[0042] A general-purpose measuring device can be used to measure the particle size and volume of crosslinked resin particles in an aqueous dispersion, and an example of such a device is the Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. In this specification, the volume average particle size of uncrosslinked resin particles can be measured by replacing "crosslinked resin particles" with "uncrosslinked resin particles" in the above method.

[0043] (Peroxide) The crosslinked structure in the present crosslinked resin particles (B) is not particularly limited, but is preferably crosslinked using a peroxide. That is, the present crosslinked resin particles (B) are preferably crosslinked using a peroxide. When a peroxide is used, radicals generated by decomposition of the peroxide act on the molecules of the resin (e.g., PHA) that constitute the resin particles. As a result, molecular chains of the resin that constitutes the resin particles are directly bonded to each other, thereby forming a crosslinked structure.

[0044] When the crosslinked resin particles (B) are crosslinked using a peroxide, the aqueous dispersion containing the crosslinked resin particles (B) may contain substances derived from the peroxide used to introduce the crosslinked structure (such as decomposition products of the peroxide and unreacted peroxide). Alternatively, when the crosslinked resin particles (B) are crosslinked using a peroxide, substances derived from the peroxide used to introduce the crosslinked structure (such as decomposition products of the peroxide and unreacted peroxide) may adhere to the surface of the resulting crosslinked resin particles (B). That is, when the present crosslinked resin particles (B) are crosslinked using a peroxide, the present crosslinked resin particles (B), the present resin composition, the present film molded product, and the present sheet molded product may contain substances derived from the peroxide (such as decomposition products of the peroxide and unreacted peroxide). When the present crosslinked resin particles (B), the present resin composition, the present film molded product, and the present sheet molded product contain substances derived from the peroxide, analysis of the crosslinked resin particles (B), the present resin composition, the present film molded product, and the present sheet molded product reveals that the crosslinked resin particles (B) are crosslinked using a peroxide.

[0045] The peroxide may be an organic peroxide or an inorganic peroxide, but is preferably an organic peroxide because it can increase the gel fraction more efficiently.

[0046] As the organic peroxide, it is preferable to use at least one selected from the group consisting of diacyl peroxides, alkyl peroxy esters, dialkyl peroxides, hydroperoxides, peroxyketals, peroxycarbonates, and peroxydicarbonates, taking into consideration the heating temperature and / or time during the crosslinking treatment.

[0047] Specific examples of such organic peroxides include butyl peroxy neododecanoate, octanoyl peroxide, dilauroyl peroxide, succinic peroxide, a mixture of toluoyl peroxide and benzoyl peroxide, benzoyl peroxide, bis(butylperoxy)trimethylcyclohexane, butyl peroxylaurate, dimethyldi(benzoylperoxy)hexane, bis(butylperoxy)methylcyclohexane, bis(butylperoxy)cyclohexane, and butylperoxybenzo ester, butyl bis(butylperoxy)valerate, dicumyl peroxide, di-t-hexyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxymethyl monocarbonate, t-pentylperoxymethyl monocarbonate, t-hexylperoxymethyl monocarbonate, t-heptylperoxymethyl monocarbonate, t-octylperoxymethyl monocarbonate, 1 , 1,3,3-tetramethylbutylperoxymethyl monocarbonate, t-butylperoxyethyl monocarbonate, t-pentylperoxyethyl monocarbonate, t-hexylperoxyethyl monocarbonate, t-heptylperoxyethyl monocarbonate, t-octylperoxyethyl monocarbonate, 1,1,3,3-tetramethylbutylperoxyethyl monocarbonate, t-butylperoxy n-propyl monocarbonate, t-pentylperoxy n-propyl monocarbonate, t-hexylperoxy peroxy isopropyl monocarbonate, t-heptylperoxy isopropyl monocarbonate, t-octylperoxy isopropyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy isopropyl monocarbonate, t-butylperoxy isopropyl monocarbonate, t-pentylperoxy isopropyl monocarbonate, t-hexylperoxy isopropyl monocarbonate, t-heptylperoxy isopropyl monocarbonate, t-octylperoxy isopropyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy isopropyl monocarbonate, t-butylperoxy n-butyl monocarbonate, t-pentylperoxy n-butyl monocarbonate, t-hexylperoxy n-butyl monocarbonate, t-heptylperoxy n-butyl monocarbonate, t-octylperoxy n-butyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy n-butyl monocarbonate, t-butylperoxy isobutyl monocarbonate, t-pentylperoxy isobutyl monocarbonate, t -Hexylperoxy isobutyl monocarbonate, t-heptylperoxy isobutyl monocarbonate, t-octylperoxy isobutyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy isobutyl monocarbonate, t-butylperoxy sec-butyl monocarbonate, t-pentylperoxy sec-butyl monocarbonate, t-hexylperoxy sec-butyl monocarbonate, t-heptylperoxy sec-butyl monocarbonate, t-octylperoxy sec-butyl monocarbonate t-butylperoxy t-butyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy sec-butyl monocarbonate, t-butylperoxy t-butyl monocarbonate, t-pentylperoxy t-butyl monocarbonate, t-hexylperoxy t-butyl monocarbonate, t-heptylperoxy t-butyl monocarbonate, t-octylperoxy t-butyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy t-butyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-pentylperoxy 2-ethylhexyl monocarbonate ethylhexyl monocarbonate, t-hexylperoxy 2-ethylhexyl monocarbonate, t-heptylperoxy 2-ethylhexyl monocarbonate, t-octylperoxy 2-ethylhexyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexyl monocarbonate, diisobutyl peroxide, cumyl peroxy neodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis(4-t-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy) Examples of organic peroxides include hexane, t-hexylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-amylperoxy-3,5,5-trimethylhexanoate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, and 2,2-di-t-butylperoxybutane. One organic peroxide may be used alone, or two or more organic peroxides may be used in combination.

[0048] Among these, t-butylperoxyisopropyl monocarbonate, t-pentylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-pentylperoxy2-ethylhexyl monocarbonate, t-hexylperoxy2-ethylhexyl monocarbonate, t-amylperoxyisopropyl monocarbonate, di-t-hexyl peroxide, t-butylperoxy2-ethylhexanoate Peroxymethylbutylperoxyisobutyrate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, and 1,1,3,3-tetramethylbutylperoxyneodecanoate are preferred organic peroxides because they can efficiently promote crosslinking of the resin that constitutes the resin particles.

[0049] Since the heating temperature during the crosslinking treatment can be set low, the peroxide is preferably a compound exhibiting a one-hour half-life temperature of 200° C. or less, more preferably a compound exhibiting a one-hour half-life temperature of 170° C. or less, and even more preferably a compound exhibiting a one-hour half-life temperature of 140° C. or less. The lower limit of the one-hour half-life temperature of the peroxide may be 50° C. or more, 60° C. or more, or 70° C. or more.

[0050] Particularly preferred organic peroxides exhibiting such a one-hour half-life temperature include t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, and 1,1,3,3-tetramethylbutylperoxyneodecanoate.

[0051] The case where the peroxide is an inorganic peroxide will be described. Examples of the inorganic peroxide include hydrogen peroxide, potassium peroxide, calcium peroxide, sodium peroxide, magnesium peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate, taking into consideration the heating temperature and / or time during the crosslinking treatment. Among these, hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate are preferred because they are easy to handle and have decomposition temperatures suitable for the heating temperature during the crosslinking treatment. The inorganic peroxide may be used alone or in combination of two or more. Furthermore, an organic peroxide and an inorganic peroxide may be used in combination.

[0052] (Polyfunctional Compound) The crosslinked structure in the present crosslinked resin particles (B) may be introduced using only a peroxide, but it is preferable that it is introduced using both a peroxide and a polyfunctional compound. That is, it is preferable that the present crosslinked resin particles (B) are crosslinked in the presence of a peroxide and a polyfunctional compound. When both a peroxide and a polyfunctional compound are used, the gel fraction of the crosslinked resin particles (B) can be increased with a smaller amount of peroxide than when only a peroxide is used.

[0053] The polyfunctional compound refers to a compound having two or more functional groups (e.g., radical reactive groups) per molecule that can crosslink the resin (e.g., PHA) that constitutes the resin particles. The polyfunctional compound is not particularly limited, but is preferably a compound that is reactive with radicals generated from peroxides, and is particularly preferably a compound having two or more radical reactive groups per molecule. The radical reactive group is preferably at least one selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group.

[0054] Such polyfunctional compounds are not particularly limited, but examples thereof include allyl (meth)acrylate, allyl alkyl (meth)acrylates, allyloxyalkyl (meth)acrylates, polyfunctional (meth)acrylates having two or more (meth)acrylic groups such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol (meth)acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. Preferably, the polyfunctional compound is one or more selected from the group consisting of allyl methacrylate, triallyl isocyanurate, butanediol di(meth)acrylate, and divinylbenzene, and more preferably, the polyfunctional compound is one or more selected from the group consisting of allyl methacrylate and triallyl isocyanurate.

[0055] When a crosslinked structure is formed in the presence of a polyfunctional compound, the resulting crosslinked resin particles (B) usually contain a structure derived from the polyfunctional compound, and in this case, the molecular chains of the resin constituting the resin particles are bonded to each other via the structure derived from the polyfunctional compound.

[0056] (Other Components) The present crosslinked resin particles (B) are crosslinked resin particles containing PHA. Therefore, the present crosslinked resin particles (B) may be crosslinked resin particles containing only PHA, or may be crosslinked resin particles containing other components other than PHA. Examples of the other components include resins other than PHA, antioxidants, hydrolysis inhibitors, antiblocking agents, crystal nucleating agents, lubricants, and ultraviolet absorbers.

[0057] The proportion of PHA in the present crosslinked resin particles (B) is not particularly limited. The content of PHA in 100% by weight of the resin component of the present crosslinked resin particles (B) may be 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, particularly preferably 95% by weight or more, and may even be 99% by weight or more. The upper limit of the content of PHA in 100% by weight of the resin component of the present crosslinked resin particles (B) is not particularly limited, as long as it is 100% by weight or less. Note that the term "resin component of the crosslinked resin particles" refers to the resin that essentially constitutes the crosslinked resin particles, and does not include components that crosslink the molecular chains of the resin (e.g., structures derived from polyfunctional compounds) or residues of components used to crosslink the molecular chains of the resin (e.g., unreacted peroxides, decomposition products of peroxides, unreacted polyfunctional compounds, etc.).

[0058] Examples of the resin other than PHA include aliphatic polyesters other than PHA and aliphatic aromatic polyesters. Examples of aliphatic polyesters other than PHA include (i) polycaprolactone (PCL), (ii) polylactic acid (PLA), and (iii) aliphatic polyesters having a structure obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid. Specific examples of the aliphatic polyesters having a structure obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid include polyethylene succinate, polybutylene succinate (hereinafter also referred to as "PBS"), polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene succinate adipate (hereinafter also referred to as "PBSA"), polyethylene sebacate, polybutylene sebacate, etc. Examples of the aliphatic aromatic polyester include aliphatic aromatic polyesters obtained by copolymerizing both an aliphatic compound and an aromatic compound as monomers (both aliphatic compounds and aromatic compounds are used as monomers). Examples of the aliphatic aromatic polyester include polybutylene adipate terephthalate (hereinafter sometimes referred to as "PBAT"), polybutylene sebacate terephthalate (hereinafter sometimes referred to as "PBSeT"), polybutylene azelate terephthalate (hereinafter sometimes referred to as "PBAzT"), polybutylene succinate terephthalate (hereinafter sometimes referred to as "PBST"), and polybutylene succinate adipate terephthalate (hereinafter sometimes referred to as "PBSAT"). These resins other than PHA may be used alone or in combination of two or more. In the crosslinked resin particles (B), the resin other than PHA may be crosslinked or uncrosslinked.

[0059] The present crosslinked resin particles (B) are different from the expanded resin particles disclosed in WO 2007 / 049694 and WO 2019 / 146555, and are preferably not expanded. In other words, the present crosslinked resin particles (B) preferably contain substantially no air bubbles inside the particles. "Substantially no air bubbles inside the particles" means that the volume of air bubbles (voids) is 10% or less of the volume of 100% of the crosslinked resin particles (B).

[0060] When the crosslinked resin particles (B) are not expanded, the apparent density of the crosslinked resin particles (B) is relatively large. The apparent density of the crosslinked resin particles (B) is 0.6 g / cm ３ It is preferable that the density exceeds 0.7 g / cm ３ More preferably, it is 0.9 g / cm or more. ３ The apparent density of the crosslinked resin particles (B) can be determined by the method described in JIS K0061 (Method for measuring density and specific gravity of chemical products) or JIS Z8807 (Method for measuring density and specific gravity of solids).

[0061] The average weight per particle of the present crosslinked resin particles (B) is not particularly limited. For example, when the volume average particle diameter of the present crosslinked resin particles (B) is 10.00 μm or less, the average weight per particle of the crosslinked resin particles (B) can be much less than 0.1 mg.

[0062] The crosslinked resin particles (B) may be dried, and the shape after drying may be powder, pellets, crumbs, a film, a sheet, or the like, depending on the drying method.

[0063] (Method for producing crosslinked resin particles (B)) An example of a method for producing the present crosslinked resin particles (B) will now be described in detail. The present crosslinked resin particles (B) can be produced by crosslinking resin molecular chains in an aqueous dispersion containing resin particles before crosslinking treatment in the presence of a peroxide.

[0064] The term "resin particles" refers to particles composed of a resin component that essentially constitutes crosslinked resin particles. When the resin component is composed only of PHA, the resin particles can also be called PHA particles. To efficiently crosslink the resin molecular chains, it is preferable to heat the aqueous dispersion of resin particles containing peroxide to a temperature suitable for decomposing the peroxide.

[0065] More specifically, the method for producing the crosslinked resin particles (B) preferably includes the steps of: (1) preparing an aqueous dispersion of resin particles in which pre-crosslinked resin particles (e.g., PHA particles) are dispersed in water; (2) adding a peroxide to the aqueous dispersion of resin particles to impregnate the resin particles with the peroxide; and (3) heating the aqueous dispersion of resin particles impregnated with the peroxide to a heating temperature to crosslink the resin molecular chains (e.g., PHA molecular chains). Furthermore, the method more preferably includes the step of maintaining the heating temperature after all the peroxide has been added.

[0066] In step (1), for example, the aqueous dispersion of PHA particles may be an aqueous dispersion obtained by culturing a PHA-producing microorganism to accumulate PHA in the cells, disrupting the cells in the culture solution, and then separating and removing the cell components, or an aqueous dispersion obtained by concentrating or diluting the aqueous dispersion. According to such a method, the process from producing PHA particles by culturing a PHA-producing microorganism to crosslinking treatment can be carried out without separating the PHA particles from water.

[0067] Alternatively, the aqueous dispersion of resin particles (for example, PHA particles) can be prepared by dispersing dried resin particles (for example, PHA particles) in water.

[0068] The aqueous medium contained in the aqueous dispersion may be water alone or a mixed solvent of water and a water-compatible organic solvent. In the mixed solvent, the concentration of the water-compatible organic solvent is not particularly limited as long as it is equal to or lower than the solubility of the organic solvent in water.

[0069] The organic solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, pentanol, hexanol, and heptanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide and acetamide; dimethyl sulfoxide; pyridine; piperidine; and the like. Among these, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, acetonitrile, and propionitrile are preferred because they are easily removable. Furthermore, methanol, ethanol, 1-propanol, 2-propanol, butanol, and acetone are more preferred because they are easily available. Furthermore, methanol, ethanol, and acetone are particularly preferred.

[0070] The water content in the entire aqueous medium (100% by weight) constituting the aqueous dispersion is preferably 5% by weight to 100% by weight. The water content in 100% by weight of the aqueous medium is more preferably 10% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 70% by weight or more. The water content in 100% by weight of the aqueous medium may be 90% by weight or more, or may be 95% by weight or more.

[0071] In the aqueous dispersion, the volume average particle diameter of the resin particles is preferably within the same range as that of the crosslinked resin particles (B) described above. In the case of PHA particles produced by a PHA-producing microorganism, the volume average particle diameter can usually be within the above range, so that an aqueous dispersion of PHA particles having a desired volume average particle diameter can be obtained without carrying out a special step for adjusting the particle diameter.

[0072] The concentration of the resin particles in the aqueous dispersion is not particularly limited and can be set appropriately, but may be, for example, about 1 to 70% by weight, and preferably about 5 to 50% by weight.

[0073] The aqueous dispersion of resin particles preferably contains a dispersant to improve the dispersibility of the resin particles and promote the crosslinking reaction uniformly. Examples of dispersants include anionic surfactants such as dioctyl sodium sulfosuccinate, sodium dodecyl sulfate, sodium lauryl sulfate, and sodium oleate; cationic surfactants such as lauryl trimethylammonium chloride; nonionic surfactants such as glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene polyoxypropylene glycol; and water-soluble polymers such as polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, and sodium polymethacrylate. These dispersants may be used alone or in combination of two or more.

[0074] When a dispersant is used, the content (addition amount) of the dispersant in the aqueous dispersion is not particularly limited. The content of the dispersant in the aqueous dispersion may be, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the resin particles.

[0075] In step (2), a peroxide is added to the aqueous dispersion of resin particles obtained in step (1) to impregnate the resin particles with the peroxide. The peroxide may be any of those described above. The peroxide may be added in various forms, such as a solid or liquid. Alternatively, a liquid diluted with a diluent may be added. The peroxide may be added all at once, continuously, or in portions.

[0076] When a peroxide and the polyfunctional compound are used in combination, it is preferable to add the polyfunctional compound to the aqueous dispersion of resin particles in step (2). The polyfunctional compound can be any of those described above. The polyfunctional compound can be added in various forms, such as solid or liquid. Alternatively, a liquid diluted with a diluent or the like may be added. The polyfunctional compound may be added all at once, continuously, or in portions.

[0077] In step (2), the resin particles are impregnated with the peroxide and any polyfunctional compound by, for example, setting the temperature of the aqueous dispersion to, for example, 0°C or higher but lower than a temperature suitable for decomposing the peroxide employed in the next step (3) after or while adding these compounds to the aqueous dispersion of the resin particles, and maintaining this temperature for, for example, about 1 minute to 5 hours while stirring the aqueous dispersion. Specifically, the temperature of the aqueous dispersion during impregnation may be about 0°C to 80°C.

[0078] The amount of peroxide used can be appropriately set in consideration of the gel fraction of the crosslinked resin particles (B), and is, for example, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, even more preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the resin particles.

[0079] According to the production method of crosslinking resin particles in an aqueous dispersion using a peroxide, crosslinking can be easily carried out while maintaining the particle size (volume) before crosslinking to obtain crosslinked resin particles (B). On the other hand, it may be difficult to achieve this in the method of crosslinking a resin by melt-kneading in the presence of a peroxide.

[0080] Furthermore, the production method in which resin particles are crosslinked in an aqueous dispersion using a peroxide has the advantage that it is easy to control the temperature rise caused by the heat generated during the crosslinking reaction, and crosslinked resin particles (B) having a safe and stable crosslinked structure (quality) can be efficiently obtained.

[0081] The amount of the polyfunctional compound used may also be appropriately determined in consideration of the gel fraction of the crosslinked resin particles (B). The amount of the polyfunctional compound used is, for example, preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, even more preferably 0.1 to 10 parts by weight, still more preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 3 parts by weight, per 100 parts by weight of the resin particles.

[0082] In step (3), the aqueous dispersion of resin particles impregnated with peroxide is heated to a temperature suitable for decomposing the peroxide. The heating temperature is preferably within a range of approximately 25°C above or below the one-hour half-life temperature of the peroxide (one-hour half-life temperature -25°C to one-hour half-life temperature +25°C). Specifically, the heating temperature is preferably 30°C to 140°C, more preferably 50°C to 135°C, and even more preferably 60°C to 130°C. This method allows the resin (e.g., PHA) to be crosslinked at a temperature lower than its melting temperature, thereby avoiding resin degradation due to heating during the crosslinking process. The melting temperature of PHA is, for example, 50°C to 210°C.

[0083] In the subsequent step (4), it is preferable to maintain the heating temperature. This allows the crosslinking reaction using the peroxide to proceed sufficiently. The time for maintaining the heating temperature is not particularly limited, but is preferably 1 minute to 15 hours, and more preferably 1 hour to 10 hours.

[0084] After the crosslinking reaction is completed, the crosslinked resin particles (B) are separated from the aqueous dispersion, and water is removed from the separated crosslinked resin particles (B) to obtain dried crosslinked resin particles (B). The method for separating the crosslinked resin particles (B) from the aqueous dispersion is not particularly limited, and examples thereof include filtration, centrifugation, heat drying, freeze drying, and spray drying. For example, spray drying can be used to obtain dried crosslinked resin particles (B) directly from the aqueous dispersion. Furthermore, by extruding the crosslinked resin particles (B) alone after separation from the aqueous dispersion, residual water can be completely removed, and crosslinked resin particles (B) can be obtained in pellet form. Furthermore, an aggregation step using a coagulant and / or adjusting the pH may be performed.

[0085] The content of the crosslinked resin particles (B) in the present film molded product or the present sheet molded product is 1 to 60 parts by weight per 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B). This configuration provides the film molded product or the present sheet molded product with the advantage of excellent tear resistance and / or impact resistance. The content of the crosslinked resin particles (B) in the present film molded product or the present sheet molded product may be 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more per 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B). The content of the crosslinked resin particles (B) in the present film molded product or the present sheet molded product is preferably 55 parts by weight or less, more preferably 53 parts by weight or less, and even more preferably 50 parts by weight or less, per 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B). The content of the crosslinked resin particles (B) in the present film molding or the present sheet molding may be 45 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 12 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B).

[0086] <Thermoplastic Resin (A)> In the present resin composition, the thermoplastic resin (A) can also be considered a matrix resin. That is, in the present film molded product or the present sheet molded product, the thermoplastic resin (A) can also be considered a matrix resin. The thermoplastic resin (A) is not particularly limited as long as it can be molded into a desired shape by melting it with heat and then cooling and solidifying it. Specific examples of the thermoplastic resin (A) include polyolefin resins such as polyethylene and polypropylene, acrylic resins such as polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, and polymethyl methacrylic acid, AS resin, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester resin, and cyclic polyolefin. These thermoplastic resins (A) may be used alone or in combination of two or more. The thermoplastic resin (A) preferably has a gel fraction of less than 50%. The thermoplastic resin (A) is preferably not crosslinked.

[0087] The thermoplastic resin (A) is particularly preferably a polyester resin, such as an aliphatic polyester (e.g., PHA, PLA, PCL, or an aliphatic polyester having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are polycondensed) or an aliphatic aromatic polyester.

[0088] Specific embodiments of the aliphatic polyester and the aliphatic aromatic polyester are the same as those described in the sections on (PHA) and (Other Components) in the section on <Crosslinked Resin Particles (B)> above, and therefore, the descriptions therein are incorporated by reference and will not be described here.

[0089] Since the crosslinked resin particles (B) contain a biodegradable PHA, it is preferable that the thermoplastic resin (A) also contain a biodegradable resin. This configuration has the advantage of increasing the biodegradability of the entire resin composition, i.e., the entire film molded body and sheet molded body. Therefore, when the thermoplastic resin (A) contains a biodegradable resin, the resin composition, film molded body, and sheet molded body are expected to be useful in addressing the problem of plastic waste and being environmentally friendly. Furthermore, when the thermoplastic resin (A) contains a biodegradable resin, the resin composition, as well as the film molded body and sheet molded body containing the resin composition, can reduce soil contamination due to disposal. This can contribute to the achievement of Sustainable Development Goals (SDGs), such as Goal 12, "Ensure sustainable consumption and production patterns." Furthermore, when the biodegradable resin contained in the thermoplastic resin (A) is marine degradable in addition to soil degradable, the present resin composition containing the present crosslinked resin particles (B), as well as the present film molded product and the present sheet molded product containing the resin composition, can suppress marine pollution in addition to suppressing soil pollution due to disposal.

[0090] Furthermore, when the crosslinked resin particles (B) contain a resin produced from a plant-derived raw material, from the viewpoint of resource circulation, it is preferable that the thermoplastic resin (A) also contains a resin produced from a plant-derived raw material, and it is more preferable that the thermoplastic resin (A) is composed only of a resin produced from a plant-derived raw material.

[0091] The case where the thermoplastic resin (A) contains a biodegradable resin will be described. The thermoplastic resin (A) preferably contains 10 to 100% by weight of the biodegradable resin, based on 100% by weight of the thermoplastic resin (A). The thermoplastic resin (A) more preferably contains 30% by weight or more of the biodegradable resin, even more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more, based on 100% by weight of the thermoplastic resin (A). The thermoplastic resin (A) may be composed solely of the biodegradable resin.

[0092] Since the film or sheet molding can fully benefit from the tear resistance and impact resistance improving effects of the crosslinked resin particles (B), the biodegradable resin contained in the thermoplastic resin (A) preferably contains a polyester resin, more preferably contains an aliphatic polyester, and particularly preferably contains PHA and / or polylactic acid. The PHA used as the thermoplastic resin (A) preferably has a gel fraction of less than 50%. The PHA used as the thermoplastic resin (A) preferably does not have a crosslinked structure.

[0093] The case where the thermoplastic resin (A) contains PHA and / or polylactic acid as a biodegradable resin will be described below. The thermoplastic resin (A) preferably contains 10% by weight to 100% by weight of PHA and polylactic acid in total, more preferably 30% by weight or more, even more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more, based on 100% by weight of the thermoplastic resin (A).

[0094] The PHA that can be used as the thermoplastic resin (A) is not particularly limited, and examples thereof include polyglycolic acid, P3HA, poly(4-hydroxyalkanoate)-based resins, etc. As the PHA, only one type may be used, or two or more types may be used in combination. As the PHA used as the thermoplastic resin (A), P3HA is particularly preferred.

[0095] A case where the crosslinked resin particles (B) contain P3HA and the thermoplastic resin (A) contains P3HA will be described. The P3HA that can be used as the thermoplastic resin (A) is the same as the P3HA related to the crosslinked resin particles (B), and the various P3HAs described above can be used. The P3HA contained in the thermoplastic resin (A) may be a resin having the same composition as the P3HA contained in the crosslinked resin particles (B), or may be a resin having a different composition and / or physical properties. The P3HA contained in the thermoplastic resin (A) is preferably a resin having a different composition and / or physical properties from the P3HA contained in the crosslinked resin particles (B), and is more preferably a resin that is harder than the P3HA contained in the crosslinked resin particles (B).

[0096] The case where the P3HA used as the thermoplastic resin (A) contains 3-hydroxybutanoic acid (3HB) repeating units will be described. In this case, from the viewpoint of the balance between flexibility and strength, the composition ratio of 3HB repeating units in the total monomer repeating units (100 mol%) of the P3HA is preferably 80 mol% to 99 mol%, more preferably 82 mol% to 97 mol%. When the composition ratio of 3HB repeating units in the P3HA is 80 mol% or more, the rigidity of the P3HA can be further improved. On the other hand, when the composition ratio of 3HB repeating units in the P3HA is 99 mol% or less, the flexibility of the P3HA tends to be further improved. Two or more types of P3HA having different composition ratios of 3HB repeating units may be used in combination.

[0097] The weight-average molecular weight of the PHA used as the thermoplastic resin (A) is not particularly limited, but is preferably 50,000 to 3,000,000, more preferably 100,000 to 2,000,000, and even more preferably 150,000 to 1,500,000. When the weight-average molecular weight of the PHA is 50,000 or more, sufficient rigidity and / or strength can be obtained in a film molded product or sheet molded product. On the other hand, a PHA having a weight-average molecular weight of 3,000,000 or less can have the advantage of being easy to manufacture and / or easy to handle in order to achieve the object of one embodiment of the present invention.

[0098] Polylactic acid usable as the thermoplastic resin (A) may be any conventionally known polylactic acid, and may be crystalline polylactic acid, amorphous polylactic acid, or a mixture of crystalline polylactic acid and amorphous polylactic acid.

[0099] The polylactic acid may be a homopolymer of lactic acid, a copolymer of lactic acid and other monomers, or a blend of a homopolymer of lactic acid and a copolymer of lactic acid and other monomers.

[0100] Examples of the other monomers include aliphatic hydroxycarboxylic acids other than lactic acid, aliphatic polyhydric alcohols, aliphatic polycarboxylic acids, and polyfunctional polysaccharides.

[0101] The lactic acid raw material for producing polylactic acid is not particularly limited, and can be L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof, or L-lactide, D-lactide, meso-lactide, or a mixture thereof, etc. Lactic acid obtained by microbial fermentation from renewable plant-derived raw materials such as starch can be suitably used.

[0102] The method for producing polylactic acid is not particularly limited, and known methods such as dehydration condensation polymerization and ring-opening polymerization can be applied.

[0103] The weight-average molecular weight of the polylactic acid used as the thermoplastic resin (A) is not particularly limited, but is preferably 50,000 to 1,000,000, more preferably 70,000 to 700,000, and even more preferably 100,000 to 400,000. When the weight-average molecular weight of polylactic acid is 50,000 or more, sufficient rigidity and / or strength can be obtained in a film or sheet molded product. On the other hand, polylactic acid having a weight-average molecular weight of 1,000,000 or less can have the advantage of being easy to produce and / or easy to handle in order to achieve the object of one embodiment of the present invention.

[0104] Regarding the PHA used as the thermoplastic resin (A), other aspects than those described above are the same as those explained in the section (PHA) above, so that the explanation therefor is incorporated by reference and will not be repeated here.

[0105] The content of the thermoplastic resin (A) in the present film molded product or the present sheet molded product is 40 to 99 parts by weight, based on 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B). This configuration provides the film molded product or the present sheet molded product with the advantage of being excellent in at least one of tear resistance and impact resistance. The content of the thermoplastic resin (A) in the present film molded product or the present sheet molded product may be 40 to 95 parts by weight, 45 to 93 parts by weight, 47 to 90 parts by weight, 50 to 80 parts by weight, 50 to 85 parts by weight, 50 to 75 parts by weight, or 50 to 70 parts by weight, based on 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B). The content of the thermoplastic resin (A) in the present film molding or the present sheet molding may be 55 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 85 parts by weight or more, 88 parts by weight or more, or 90 parts by weight or more, based on 100 parts by weight of the total of the thermoplastic resin (A) and the crosslinked resin particles (B).

[0106] <Crystal Nucleating Agent> The present resin composition may further contain a crystal nucleating agent. In other words, the present film molding or the present sheet molding may further contain a crystal nucleating agent. When the thermoplastic resin composition contains a crystal nucleating agent, if the thermoplastic resin (A) is a crystalline resin, crystallization during molding is promoted, and molding processability, productivity, etc. can be improved. When the present film molding or the present sheet molding contains a crystal nucleating agent, there is also the advantage that the present film molding or the present sheet molding has excellent heat resistance or mechanical properties.

[0107] The crystal nucleating agent is not particularly limited, and conventionally known ones can be used. Examples of the crystal nucleating agent include inorganic substances such as talc, kaolinite, montmorillonite, mica, synthetic mica, clay, zeolite, silica, carbon black, graphite, boron nitride, zinc oxide, titanium oxide, tin oxide, calcium carbonate, magnesium carbonate, aluminum oxide, neodymium oxide, barium sulfate, sodium chloride, and metal phosphates; sugar alcohol compounds derived from natural products such as erythritol, pentaerythritol, galactitol, mannitol, and arabitol; polysaccharides such as chitin and chitosan; polyols such as aliphatic alcohols (polyols), polyvinyl alcohol, and polyethylene oxide; sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, and terephthalic acid salts. metal salts of organic carboxylic acids such as potassium phosphate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, and sodium cyclohexanecarboxylate; organic sulfonates such as sodium p-toluenesulfonate and sodium sulfoisophthalate;Carboxylic acid amides such as ethylene stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, and trimesic acid tris(t-butylamide), lauric acid esters, palmitic acid esters, oleic acid esters, stearic acid esters, erucic acid esters, N-oleyl palmitic acid ester, N-oleyl oleic acid ester, N-oleyl stearate, N-stearyl oleic acid ester, N-stearyl stearate, N-stearyl erucic acid ester, methylene bisstearate, ethylene bislauric acid ester, ethylene biscapric acid ester, ethylene bisoleic acid ester, ethylene bisstearate, ethylene biserucic acid ester, ethylene Examples of suitable crystal nucleating agents include carboxylic acid esters such as butylene bisisostearate, butylene bisstearate, and p-xylylene bisstearate; dicarboxylic acid derivatives such as dimethyl adipate, dibutyl adipate, diisodecyl adipate, and dibutyl sebacate; cyclic compounds having a functional group C═O and one or more functional groups selected from the group consisting of NH, S, and O in the molecule, such as indigo, quinacridone, and quinacridone magenta; sorbitol derivatives such as bisbenzylidene sorbitol and bis(p-methylbenzylidene)sorbitol; compounds containing a nitrogen-containing heteroaromatic nucleus, such as pyridine, triazine, and imidazole; phosphate ester compounds, bisamides of higher fatty acids, and metal salts of higher fatty acids; branched polylactic acid; and low-molecular-weight poly(3-hydroxybutyrate). These crystal nucleating agents may be used alone or in combination of two or more.

[0108] The content of the nucleating agent is not particularly limited as long as it can promote the crystallization of the thermoplastic resin (A). The content of the nucleating agent is preferably 0.05 to 12.00 parts by weight, more preferably 0.10 to 10.00 parts by weight, and even more preferably 0.50 to 8.00 parts by weight, per 100 parts by weight of the thermoplastic resin (A). When the content of the nucleating agent is within the above range, the effect of the nucleating agent can be obtained while suppressing a decrease in viscosity during molding and physical properties of the molded product.

[0109] <Lubricant> The present resin composition may further contain a lubricant. In other words, the present film molded body or the present sheet molded body may further contain a lubricant. When the present film molded body or the present sheet molded body contains a lubricant, the surface smoothness of the film molded body or the present sheet molded body can be improved.

[0110] The lubricant is not particularly limited. Examples of the lubricant include, but are not limited to, fatty acid metal salts such as magnesium stearate and calcium stearate; fatty acid amides such as behenic acid amide, stearic acid amide, erucic acid amide, oleic acid amide, methylene bis-stearic acid amide, and ethylene bis-stearic acid amide; polyethylene wax, oxidized polyester wax, glycerin mono-fatty acid esters such as glycerin monostearate, glycerin monobehenate, and glycerin monolaurate; organic acid monoglycerides such as succinic acid saturated fatty acid monoglycerides; sorbitan fatty acid esters such as sorbitan behenate, sorbitan stearate, and sorbitan laurate; polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, tetraglycerin stearate, tetraglycerin laurate, decaglycerin stearate, and decaglycerin laurate; and higher alcohol fatty acid esters such as stearyl stearate. Lubricants may be used alone or in combination of two or more.

[0111] The content of the lubricant (when multiple lubricants are used, the total content) is not particularly limited as long as it can impart lubricity to the film or sheet molded body. The content of the lubricant is preferably 0.01 to 20.00 parts by weight, more preferably 0.05 to 10.00 parts by weight, even more preferably 0.10 to 10.00 parts by weight, even more preferably 0.20 to 5.00 parts by weight, and particularly preferably 0.30 to 4.00 parts by weight, per 100 parts by weight of the thermoplastic resin (A). When the content of the lubricant is within the above range, it is possible to obtain the effect of the lubricant while avoiding bleeding out of the lubricant onto the molded body surface.

[0112] <Other Components> The present film molding or the present sheet molding may contain other components such as plasticizers; organic fillers; inorganic fillers; antioxidants; hydrolysis inhibitors; ultraviolet absorbers; colorants such as dyes and pigments; and antistatic agents, to the extent that their functions are not impaired.

[0113] The plasticizer is not particularly limited. Examples of the plasticizer include polyester-based plasticizers such as polypropylene glycol sebacate ester; aliphatic dibasic acid ester-based plasticizers such as di-1-butyl adipate, di-n-butyl sebacate, and di-2-ethylhexyl azelate; glycerin-based plasticizers such as glycerin diacetomonolaurate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate; polycarboxylic acid ester-based plasticizers such as tri-2-ethylhexyl acetylcitrate and tributyl acetylcitrate; polyolefin plasticizers such as polyethylene glycol, polypropylene glycol, poly(ethylene oxide-propylene oxide) block and / or random copolymers, and polytetramethylene glycol. alkylene glycol-based plasticizers; phosphate ester-based plasticizers such as diphenyl-2-ethylhexyl phosphate and diphenyloctyl phosphate; epoxy-based plasticizers such as epoxidized soybean oil and epoxidized linseed oil fatty acid butyl esters; and castor oil-based plasticizers such as castor oil fatty acid esters, methyl ricinoleate, ethyl ricinoleate, isopropyl ricinoleate, butyl ricinoleate, ethylene glycol monoricylate, propylene glycol monoricylate, trimethylolpropane monoricylate, sorbitan monoricylate, castor oil fatty acid polyethylene glycol esters, castor oil ethylene oxide adducts, castor oil-based polyols, castor oil-based toluene, and castor oil-based diols. These plasticizers may be used alone or in combination of two or more.

[0114] The organic filler is not particularly limited. Examples of the organic filler include fillers made of naturally-derived materials such as wood-based materials (e.g., wood chips, wood flour, sawdust, etc.), rice husks, rice flour, starch, corn starch, rice straw, wheat straw, and natural rubber; organic fibers such as natural plant fibers, natural animal fibers, and synthetic fibers; and fillers made of synthetic resin materials such as polyester, polyacrylic, polyamide, nylon, polyethylene, polyolefin, polyvinyl alcohol, polyvinyl chloride, polyurethane, polyacetal, aramid, PBO (poly-p-phenylene benzobisoxazole), polyphenylene sulfide, acetyl cellulose, polybenzazole, polyarylate, polyvinyl acetate, and synthetic rubber.

[0115] The natural plant fibers are not particularly limited. Examples of the natural plant fibers include kenaf fiber, abaca fiber, bamboo fiber, jute fiber, hemp fiber, linen fiber, henequen (sisal), ramie fiber, hemp, cotton, banana fiber, coconut fiber, palm, paper mulberry, Mitsumata, bagasse, etc. Other examples include regenerated fibers such as pulp, cellulose fiber, and rayon processed from plant fibers. Examples of natural animal fibers include wool, silk, cashmere, and mohair.

[0116] The inorganic filler is not particularly limited. Examples of the inorganic filler include silica-based inorganic fillers (e.g., quartz, fumed silica, silicic anhydride, fused silica, crystalline silica, amorphous silica, fillers formed by condensing alkoxysilanes, ultrafine amorphous silica, etc.), alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass, silicone rubber, silicone resin, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, and silver powder. These inorganic fillers may be surface-treated to improve dispersibility in the resin composition. These inorganic fillers may be used alone or in combination of two or more.

[0117] The antioxidant is not particularly limited. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These antioxidants may be used alone or in combination of two or more.

[0118] The hydrolysis inhibitor is not particularly limited. Examples of the hydrolysis inhibitor include carbodiimide compounds, epoxy compounds, isocyanate compounds, and oxazoline compounds. These hydrolysis inhibitors may be used alone or in combination of two or more.

[0119] The ultraviolet absorber is not particularly limited. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, salicylic acid compounds, cyanoacrylate compounds, and nickel complex salt compounds. These ultraviolet absorbers may be used alone or in combination of two or more.

[0120] The colorants such as pigments and dyes are not particularly limited. Examples of the colorants include inorganic colorants such as titanium oxide, calcium carbonate, chromium oxide, cuprous oxide, calcium silicate, iron oxide, carbon black, graphite, titanium yellow, and cobalt blue; soluble azo pigments such as lake red, lithol red, and brilliant carmine; insoluble azo pigments such as dinitrile orange and fast yellow; phthalocyanine pigments such as monochlorophthalocyanine blue, polychlorophthalocyanine blue, and polybromophthalocyanine green; condensed polycyclic pigments such as indigo blue, perylene red, isoindolinone yellow, and quinacridone red; and dyes such as oracet yellow. These colorants may be used alone or in combination of two or more.

[0121] The antistatic agent is not particularly limited. Examples of the antistatic agent include low molecular weight antistatic agents such as fatty acid ester compounds, aliphatic ethanolamine compounds, and aliphatic ethanolamide compounds, and polymeric antistatic agents. These antistatic agents may be used alone or in combination of two or more.

[0122] Furthermore, the present film molded product or the present sheet molded product may contain any of the following additives: catalyst deactivators (hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyamine compounds, hydrazine derivative compounds, phosphorus compounds, etc.), mold release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide, polyethylene wax, etc.), color inhibitors (phosphites, hypophosphites, etc.), silane coupling agents (epoxy silane coupling agents, amino silane coupling agents, (meth)acrylic silane coupling agents, isocyanate silane coupling agents, etc.), flame retardants (red phosphorus, phosphate esters, brominated polystyrene, brominated polyphenylene ether The adhesive composition may also contain: hydroxybenzoates, brominated polycarbonates, aluminum hydroxide, magnesium hydroxide, melamine and cyanuric acid or salts thereof, silicon compounds, etc.; conductive agents (carbon black, etc.); sliding property improvers (graphite, fluororesins, etc.); epoxy compounds (glycidyl ether compounds, glycidyl ester compounds, polymer compounds grafted or copolymerized with a glycidyl compound, etc.); acid anhydride compounds (maleic anhydride, succinic anhydride, polymer compounds grafted or copolymerized with an acid anhydride, etc.); carbodiimide compounds (N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, polycarbodiimide, etc.);

[0123] The content of each of the other components described above is not particularly limited as long as the effect of one embodiment of the present invention is exhibited, and can be appropriately determined by a person skilled in the art.

[0124] <Physical Properties of Thermoplastic Resin Composition> The resin composition satisfies one or more of the following (A) to (C): (A) The Elmendorf tear strength measured by the method shown in (A1) to (A4) below is 3 N / mm or more: (A1) The thermoplastic resin composition is molded into a film having a thickness of 40 μm to obtain a film molded body; (A2) The film molded body obtained in (A1) is aged for 7 days under conditions of 23°C and 50% RH; (A3) The tear strength (unit: N) of the aged film molded body is measured by a method in accordance with JIS K7128-2; (A4) The tear strength measured in (A3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (B) The Elmendorf tear strength measured by the method shown in (B1) to (B4) below is 3 N / mm or more: (B1) The thermoplastic resin composition is molded into a film having a thickness of 50 μm to 100 μm to obtain a film molded body; (B2) The film molded body obtained in (B1) is aged for 7 days under conditions of 23°C and 50% RH; (B3) The tear strength (unit: N) of the aged film molded body is measured using a method in accordance with JIS K7128-2; (B4) The tear strength measured in (B3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (C) The Elmendorf tear strength measured by the methods shown in (C1) to (C4) below is 5 N / mm or more: (C1) The thermoplastic resin composition is molded into a film having a thickness of more than 100 μm and not more than 120 μm to obtain a film molded body; (C2) The film molded body obtained in (C1) is aged for 7 days under conditions of 23°C and 50% RH; (C3) The tear strength (unit: N) of the film molded article after aging is measured by a method in accordance with JIS K7128-2; (C4) The tear strength measured in (C3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength.

[0125] Therefore, the present film molded article or the present sheet molded article obtained by molding the present resin composition has the advantage of excellent tear resistance.

[0126] In the above (A), the Elmendorf tear strength measured by the method shown in (A1) to (A4) is 3 N / mm or more, preferably 4 N / mm or more, more preferably 5 N / mm or more, more preferably 6 N / mm or more, more preferably 7 N / mm or more, even more preferably 8 N / mm or more, and particularly preferably 10 N / mm or more. In one embodiment of the present invention, if the Elmendorf tear strength measured by the method shown in (A1) to (A4) using the resin composition is 3 N / mm or more, there is an advantage in that the tear resistance, specifically the tear strength, is excellent.

[0127] In the above (B), the Elmendorf tear strength measured by the method shown in (B1) to (B4) is 3 N / mm or more, preferably 4 N / mm or more, more preferably 5 N / mm or more, more preferably 6 N / mm or more, more preferably 7 N / mm or more, even more preferably 8 N / mm or more, and particularly preferably 10 N / mm or more. In one embodiment of the present invention, if the Elmendorf tear strength measured by the method shown in (B1) to (B4) using the resin composition is 3 N / mm or more, there is an advantage in that the tear resistance, specifically the tear strength, is excellent.

[0128] In the above (C), the Elmendorf tear strength measured by the methods shown in (C1) to (C4) is preferably 5 N / mm or more, more preferably 6 N / mm or more, more preferably 7 N / mm or more, more preferably 8 N / mm or more, even more preferably 9 N / mm or more, and particularly preferably 10 N / mm or more. In one embodiment of the present invention, if the Elmendorf tear strength measured by the methods shown in (C1) to (C4) using the resin composition is 5 N / mm or more, there is an advantage in that the tear resistance, specifically the tear strength, is excellent.

[0129] In one embodiment of the present invention, the Elmendorf tear strength of a film or sheet molded article may be measured in the MD direction (the flow direction of the molten resin) or the TD direction (the direction perpendicular to the flow of the molten resin). When there is no flow direction of the molten resin, the measurement can be performed without limiting the measurement direction.

[0130] The present resin composition has a puncture impact strength of 0.3 J or more as measured by the above-described method. Therefore, the present film molding or the present sheet molding obtained by molding the present resin composition has the advantage of excellent impact resistance. The puncture impact strength of the present resin composition as measured by the above-described method is 0.3 J or more, preferably 0.7 J or more, more preferably 0.9 J or more, and even more preferably 1.2 J or more. If the puncture impact strength of the present film molding or the present sheet molding is 0.3 J or more, it has the advantage of excellent impact resistance, specifically, puncture impact strength.

[0131] (Method for producing thermoplastic resin composition) The resin composition can be produced by a known method. Specifically, the thermoplastic resin (A), crosslinked resin particles (B), and optional components such as a crystal nucleating agent, a lubricant, and other components can be melt-kneaded using an extruder, kneader, Banbury mixer, kneading roll, or the like. When melt-kneading, it is preferable to mix the components while taking care to avoid a decrease in molecular weight due to thermal decomposition. Alternatively, the thermoplastic resin composition can be produced by dissolving all raw materials (components) in a soluble solvent and then removing the solvent.

[0132] When producing a thermoplastic resin composition by melt-kneading, each component may be charged individually into an extruder, etc., or each component may be mixed in advance and the resulting mixture may be charged into an extruder, etc. For example, an aqueous dispersion of the thermoplastic resin (A) and an aqueous dispersion of the crosslinked resin particles (B) may be mixed, and then the resulting mixture may be dried in a dryer to obtain a mixed powder, which may then be charged into an extruder, etc.

[0133] When melt-kneading is performed using an extruder, the obtained thermoplastic resin composition may be extruded from the extruder into a strand shape and then cut, thereby processing the thermoplastic resin composition into particle shapes such as a bar shape, a cylindrical shape, an elliptical cylindrical shape, a sphere shape, a cube shape, a rectangular parallelepiped shape, or the like.

[0134] The resin temperature during melt-kneading cannot be generally defined because it depends on the melting point and melt viscosity of the resin used, etc. The resin temperature is preferably 140°C to 250°C, more preferably 150°C to 230°C, and even more preferably 160°C to 210°C, from the viewpoint of uniformly dispersing the crosslinked resin particles (B) in the thermoplastic resin (A) while avoiding thermal decomposition of the thermoplastic resin (A).

[0135] <Method for producing film or sheet molded article> The present film or sheet molded article can be produced by a known method. Specific examples of the molding method include inflation molding, extrusion molding, calendar molding, T-die extrusion molding, casting, rolling, pressing, injection blow molding, vacuum molding, and injection molding. Among these, the present film or sheet molded article is preferably molded by inflation molding, extrusion molding, calendar molding, T-die extrusion molding, casting, rolling, or pressing. A film or sheet molded article obtained by molding a thermoplastic resin composition can also be said to be a film or sheet molded article containing a thermoplastic resin composition.

[0136] By carrying out the above-described molding method, a molded product, specifically a sheet molded product or a film molded product, which is excellent in at least one of tear resistance and impact resistance, can be produced with good productivity.

[0137] The inflation molding method is a molding method in which a molten resin composition is extruded into a tube shape from an extruder equipped with a cylindrical die at the tip, and immediately thereafter, gas is blown into the tube to inflate it into a balloon shape, thereby forming a tubular single-layer or multi-layer film.

[0138] The calender molding method is a molding method in which a resin raw material that has been heated in advance to a molten state is sandwiched between a plurality of rolls and rolled to form a film or a sheet.

[0139] The T-die extrusion molding method is a molding method in which a thermoplastic resin composition heated to a molten state in an extruder is discharged from a T-die outlet attached to the extruder to obtain a sheet-like thermoplastic resin in a molten state, and then the sheet-like thermoplastic resin is sandwiched between a pair of smoothing rolls and taken up, thereby being cooled and solidified into a film or sheet.

[0140] <Impact Resistance of Film Molded Product or Sheet Molded Product> In one embodiment of the present invention, the lower limit of the thickness of the film molded product or sheet molded product is not particularly limited, but may be 5 μm, 6 μm, 7 μm, 8 μm, or 10 μm. In one embodiment of the present invention, the upper limit of the thickness of the film molded product or sheet molded product is not particularly limited, but may be 1000 μm, 900 μm, 800 μm, 500 μm, or 450 μm.

[0141] In one embodiment of the present invention, as described above, the upper limit of the thickness of the film molded body is less than 0.25 mm, i.e., less than 250 μm. In one embodiment of the present invention, the lower limit of the thickness of the film molded body is not particularly limited, but may be 5 μm, 6 μm, 7 μm, 8 μm, or 10 μm.

[0142] In one embodiment of the present invention, as described above, the lower limit of the thickness of the sheet molded body is 0.25 mm or more, i.e., 250 μm or more. In one embodiment of the present invention, the upper limit of the thickness of the sheet molded body is not particularly limited, but may be 1000 μm, 900 μm, 800 μm, 500 μm, or 450 μm.

[0143] The tensile impact strength of the film molded product or the sheet molded product is 100 kJ / m ２ More than 200 kJ / m is preferable. ２ More preferably, 300 kJ / m or more ２ More preferably, 400 kJ / m or more ２The tensile impact strength of the film molded product or the sheet molded product is particularly preferably 100 kJ / m or more. ２ If the thickness is above this, there is an advantage that the impact resistance, specifically the tensile impact strength, is excellent.

[0144] The film or sheet molded article can be suitably used in fields such as agriculture, fisheries, forestry, horticulture, medicine, hygiene products, the food industry, clothing, non-clothing, packaging, automobiles, building materials, etc. The film or sheet molded article can be suitably used for applications such as garbage bags, shopping bags, packaging bags for vegetables and fruits, pillow packaging, delivery bags, agricultural mulch film, fumigation sheets for forestry, binding tape including flat yarns, film for wrapping plant roots, diaper back sheets, packaging sheets, shopping bags, draining bags, and other compost bags.

[0145] An embodiment of the present invention may have the following configuration.

[0146] [X1] A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more [where the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight], the thermoplastic resin composition satisfying any one or more of the following (A) to (C): (A) The Elmendorf tear strength measured by the methods shown in (A1) to (A4) below is 3 N / mm or more: (A1) The thermoplastic resin composition is molded into a film having a thickness of 40 μm to obtain a film molded product; (A2) The film molded product obtained in (A1) is aged for 7 days under conditions of 23°C and 50% RH; (A3) The film molded product after aging is measured according to JIS (A4) The tear strength (unit: N) is measured by a method in accordance with JIS K7128-2; (A3) The tear strength measured in (A4) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (B) The Elmendorf tear strength measured by the methods shown in (B1) to (B4) below is 3 N / mm or more: (B1) The thermoplastic resin composition is molded into a film having a thickness of 50 μm to 100 μm to obtain a film molded body; (B2) The film molded body obtained in (B1) is aged for 7 days under conditions of 23°C and 50% RH; (B3) The tear strength (unit: N) of the aged film molded body is measured by a method in accordance with JIS K7128-2; (B4) The tear strength measured in (B3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (C) The thermoplastic resin composition has an Elmendorf tear strength of 5 N / mm or more as measured by the following methods (C1) to (C4): (C1) The thermoplastic resin composition is molded into a film having a thickness of more than 100 μm and not more than 120 μm to obtain a film molded body; (C2) The film molded body obtained in (C1) is aged for 7 days under conditions of 23°C and 50% RH;(C3) The tear strength (unit: N) of the film molded article after aging is measured by a method in accordance with JIS K7128-2; (C4) The tear strength measured in (C3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength;

[0147] [X2] A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more [wherein the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight], the thermoplastic resin composition having an impact energy of 0.3 J or more at the maximum impact force point in a puncture impact test measured by the following methods (1) to (3): (1) The thermoplastic resin composition is molded into a sheet having a thickness of 900 μm to obtain a sheet molded product; (2) The sheet molded product obtained in step (1) is aged for 7 days under conditions of 23°C and 50% RH, and then cut into a shape of 60 mm x 60 mm; (3) The cut-out sheet molded product is subjected to ASTM The impact energy (J) at the maximum impact force point is measured using a method in accordance with D3763-15 at a test temperature of 23°C and a test speed of 3 m / sec.

[0148] [X3] The film or sheet molded article according to [X1] or [X2], wherein the polyhydroxyalkanoate resin is a poly(3-hydroxyalkanoate) resin.

[0149] [X4] The film or sheet molding according to any one of [X1] to [X3], wherein the volume average particle diameter of the crosslinked resin particles (B) is 0.10 μm to 10.00 μm.

[0150] [X5] The film or sheet molding according to any one of [X1] to [X4], wherein the crosslinked resin particles (B) are crosslinked using a peroxide.

[0151] [X6] The film or sheet molded article according to [X5], wherein the crosslinked resin particles (B) are crosslinked in the presence of the peroxide and a polyfunctional compound.

[0152] [X7] The film or sheet molding according to any one of [X1] to [X6], wherein the crosslinked resin particles (B) are not foamed.

[0153] [X8] The film or sheet molded article according to any one of [X1] to [X7], wherein the thermoplastic resin (A) includes a biodegradable resin.

[0154] [X9] The film or sheet molded article according to [X8], wherein the biodegradable resin includes a polyester resin.

[0155] [X10] The film or sheet molded product according to any one of [X1] to [X9], further comprising a crystal nucleating agent and / or a lubricant.

[0156] [X11] The film or sheet molding is formed by an inflation molding method, an extrusion molding method, a calendar molding method, a T-die extrusion molding method, a cast method, a roll method, or a press method. [X1] to [X10] Any one of the film or sheet moldings described above.

[0157] An embodiment of the present invention may have the following configuration.

[0158] [Y1] A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (where the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), the thermoplastic resin composition having an Elmendorf tear strength of 3 N / mm or more as measured by the following methods (1) to (4): (1) The thermoplastic resin composition is molded into a film having a thickness of 40 μm to obtain a film molded product; (2) The film molded product obtained in step (1) is aged for 7 days under conditions of 23°C and 50% RH; (3) The tear strength (unit: N) of the aged film molded product is measured by a method in accordance with JIS K7128-2; (4) The tear strength measured in (3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength.

[0159] [Y2] A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) comprising a polyhydroxyalkanoate resin and having a gel fraction of 50% or more [wherein the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight], the thermoplastic resin composition having an impact energy of 0.3 J or more at the maximum impact force point in a puncture impact test measured by the following methods (1) to (3): (1) The thermoplastic resin composition is molded into a sheet having a thickness of 900 μm to obtain a sheet molded product; (2) The sheet molded product obtained in step (1) is aged for 7 days under conditions of 23°C and 50% RH, and then cut into a shape of 60 mm x 60 mm; (3) The cut-out sheet molded product is subjected to ASTM The impact energy (J) at the maximum impact force point is measured using a method in accordance with D3763-15 at a test temperature of 23°C and a test speed of 3 m / sec.

[0160] [Y3] The film or sheet molded article according to [Y1] or [Y2], wherein the polyhydroxyalkanoate resin is a poly(3-hydroxyalkanoate) resin.

[0161] [Y4] The film or sheet molding according to any one of [Y1] to [Y3], wherein the volume average particle diameter of the crosslinked resin particles (B) is 0.10 μm to 10.00 μm.

[0162] [Y5] The film or sheet molding according to any one of [Y1] to [Y4], wherein the crosslinked resin particles (B) are crosslinked using a peroxide.

[0163] [Y6] The film or sheet molded article according to [Y5], wherein the crosslinked resin particles (B) are crosslinked in the presence of the peroxide and a polyfunctional compound.

[0164] [Y7] The film or sheet molding according to any one of [Y1] to [Y6], wherein the crosslinked resin particles (B) are not foamed.

[0165] [Y8] The film or sheet molded article according to any one of [Y1] to [Y7], wherein the thermoplastic resin (A) includes a biodegradable resin.

[0166] [Y9] The film or sheet molded article according to [Y8], wherein the biodegradable resin includes a polyester resin.

[0167] [Y10] The film or sheet molded article according to any one of [Y1] to [Y9], further comprising a crystal nucleating agent and / or a lubricant.

[0168] [Y11] The film or sheet molding according to any one of [Y1] to [Y10], wherein the film or sheet molding is formed by inflation molding, extrusion molding, calendar molding, T-die extrusion molding, casting, rolling, or pressing.

[0169] EXAMPLES The following examples will be used to more specifically explain one embodiment of the present invention, but the present invention is not limited to these examples in any way.

[0170] [1] Measurement Conditions 1-1. Weight-Average Molecular Weight The resin to be measured was added to chloroform, and the resulting mixture was heated in a 60°C hot water bath for 30 minutes. The resulting mixture (chloroform solution) was filtered through a disposable PTFE filter with a 0.45 μm pore size. The resulting filtrate was then subjected to GPC measurement under the following conditions to determine the weight-average molecular weight. GPC Measurement Apparatus: Shimadzu High-Performance Liquid Chromatograph 20A System Columns: Showa Denko K-G 4A (1 column), K-806M (2 columns) Sample Concentration: 1 mg / ml Free Solution: Chloroform Solution Free Solution Flow Rate: 1.0 ml / min Sample Injection Volume: 100 μL Analysis Time: 30 minutes Standard Sample: Standard Polystyrene.

[0171] 1-2. Volume-average particle diameter The volume-average particle diameter of the crosslinked resin particles (B) was measured using an aqueous dispersion of the crosslinked resin particles (B) as a sample. A Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. was used as the measuring device. Specifically, the particle diameter and volume of each crosslinked resin particle (B) in the aqueous dispersion of the crosslinked resin particles (B) were measured using the above-mentioned device, and the volume-average particle diameter was calculated from the measurement results based on the above-mentioned formula (1), i.e., formula (2).

[0172] 1-3. Gel Fraction Dried crosslinked resin particles (B) were added to chloroform to a concentration of 0.7 wt % and maintained at 60°C for 30 minutes to obtain a chloroform solution. After allowing to stand at room temperature for 3 hours, the chloroform solution was filtered through a membrane filter with a pore size of 0.45 μm. Losses were prevented by pouring chloroform over the inside of the container and the filter multiple times while thoroughly washing. The gel remaining on the filter was dried and weighed together with the filter, and the gel fraction was calculated using the following formula: Gel fraction = ((weight of filter including dried gel - weight of filter only) / weight of crosslinked resin particles (B) used in measurement) x 100 (%).

[0173] 1-4. Tensile Impact Strength A 500 μm thick sheet molded article prepared by the method described below was aged for 7 days under conditions of 23°C and 50% RH, and then punched out into a shape conforming to JIS K 71603 to prepare a test specimen. A tensile impact test was carried out on the test specimen according to the method conforming to JIS K 7160 A method.

[0174] 1-5. Elmendorf tear strength The Elmendorf tear strength of the thermoplastic resin compositions of each Example and Comparative Example was measured by the following methods (1) to (4): (1) The thermoplastic resin composition was molded into a film having a thickness of 40 μm to 120 μm to obtain a film molded body; (2) The film molded body obtained in step (1) was aged for 7 days under conditions of 23°C and 50% RH; (3) The tear strength (unit: N) of the aged film molded body was measured by a method in accordance with JIS K7128-2; (4) The tear strength measured in (3) was divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength.

[0175] The measuring device used was a light load tear tester ("No. 2037 special specification machine" manufactured by Kumagai Riki Kogyo Co., Ltd.) having functions and a structure conforming to the standard Elmendorf tear tester specified in JIS K7128-2.

[0176] Furthermore, for each film molded article, when a flow direction of the molten resin existed, the Elmendorf tear strength was measured in both the MD direction (the flow direction of the molten resin (which can also be said to be the extrusion direction)) and the TD direction (the direction perpendicular to the flow of the molten resin (which can also be said to be the direction perpendicular to the extrusion direction)). When a flow direction of the molten resin did not exist, such as in a film molded article produced by press molding, the measurement direction was not particularly limited.

[0177] 1-6. Puncture Impact Strength For the thermoplastic resin compositions of each Example and Comparative Example, the impact energy (puncture impact strength) at the maximum impact point in a puncture impact test was measured by the methods shown in (1) to (3) below: (1) The thermoplastic resin composition was molded into a sheet having a thickness of 900 μm to obtain a sheet molded body; (2) The sheet molded body obtained in step (1) was aged for 7 days under conditions of 23°C and 50% RH, and then cut into a shape of 60 mm x 60 mm; (3) The impact energy (J) at the maximum impact point was measured for the cut-out sheet molded body using a method in accordance with ASTM D3763-15 at a test temperature of 5°C and a test speed of 2 m / s, or at a test temperature of 23°C and a test speed of 3 m / s.

[0178] The fracture mode was evaluated based on the obtained results. Specifically, when the sheet molding fractured without plastic deformation, the fracture mode was judged to be "brittle," and when the sheet molding fractured with plastic deformation, the fracture mode was judged to be "ductile."

[0179] [2] Evaluation of polyhydroxyalkanoate resins 2-1. Raw materials for crosslinked resin particles (B) 2-1-1. Uncrosslinked resin particles PHA-1: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate): Repeating unit composition; (3-hydroxybutyrate) / (3-hydroxyhexanoate)=72 / 28 (mol / mol), weight average molecular weight Mw; 500,000 to 1,500,000 PHA-2: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate): Repeating unit composition; (3-hydroxybutyrate) / (3-hydroxyhexanoate)=75 / 25 (mol / mol), weight average molecular weight Mw; 600,000 to 1,500,000 The weight average molecular weights of the resins were measured by the method described above.

[0180] 2-1-2. Peroxide Di-sec-butyl peroxydicarbonate ("Luperox (registered trademark) 225" manufactured by Arkema Yoshitomi Co., Ltd., 1-hour half-life temperature: 69°C).

[0181] 2-1-3. Polyfunctional compounds: triallyl isocyanurate.

[0182] 2-2-1. Method for Producing Crosslinked Resin Particles (B-1) (Production Example 1) Crosslinked resin particles (B-1) were produced according to the procedure described below. An aqueous dispersion (100 parts by weight of solids) of uncrosslinked resin particles (PHA-1) dispersed in water, 200 parts by weight of deionized water, 2 parts by weight of peroxide, 1 part by weight of sodium dioctyl sulfosuccinate, and 0.5 parts by weight of a polyfunctional compound were added to an autoclave or glass container equipped with a stirrer, baffle, nitrogen inlet / outlet, and thermometer to prepare an aqueous dispersion. Stirring of the resulting aqueous dispersion was initiated at room temperature (25±5°C), and simultaneously, the autoclave or glass container was purged with nitrogen. The aqueous dispersion in the autoclave or glass container was then stirred for 1 hour at room temperature, allowing the peroxide and polyfunctional compound to be impregnated into the interior of the uncrosslinked resin particles.

[0183] Thereafter, the aqueous dispersion was heated to 75° C. After the temperature reached 75° C., the reaction was carried out for 3.5 hours while maintaining the temperature, thereby obtaining an aqueous dispersion in which crosslinked resin particles (B-1) were dispersed in water.

[0184] After adjusting the pH of the aqueous dispersion, the dispersion was dried in an oven to obtain solidified crosslinked resin particles (B-1).

[0185] The volume average particle size and gel fraction of the resulting crosslinked resin particles (B-1) were measured by the above-mentioned methods, and the volume average particle size of the resulting crosslinked resin particles (B-1) was 1.70 μm and the gel fraction was 95%.

[0186] 2-2-2. Method for producing crosslinked resin particles (B-2) (Production Example 2) Crosslinked resin particles (B-2) were obtained in the same manner as in Production Example 1, except that the uncrosslinked resin particles (PHA-1) were replaced with uncrosslinked resin particles (PHA-2).

[0187] The volume average particle size and gel fraction of the resulting crosslinked resin particles (B-2) were measured by the methods described above. The volume average particle size of the resulting crosslinked resin particles (B-2) was 1.10 μm, and the gel fraction was 96%.

[0188] 2-2-3. Method for Producing Crosslinked Resin Particles (B-3) (Production Example 3) The aqueous dispersion of the crosslinked resin particles (B-1) obtained in Production Example 1 was mixed with an aqueous dispersion of silica particles (Snowtex ZL, manufactured by Nissan Chemical Industries, Ltd.) so that the ratio of the aqueous dispersion of crosslinked resin particles (B-1) to the aqueous dispersion of silica particles was 90.9% by weight / 9.1% by weight, calculated on solid content, and the pH of the resulting mixture was adjusted. The resulting mixture was then spray-dried in an OD-50 spray dryer manufactured by Okawara Kakoki Co., Ltd. under conditions of a hot air temperature of 150°C, an exhaust air temperature of 70°C, and a disk rotation speed of 10,000 rpm. Through this operation, crosslinked resin particles containing silica particles were obtained. The resulting "crosslinked resin particles containing silica particles" were used in this example as "crosslinked resin particles (B-3)."

[0189] The crosslinked resin particles in the obtained crosslinked resin particles (B-3) are the crosslinked resin particles (B-1) obtained in Production Example 1, and therefore the volume average particle diameter of the crosslinked resin particles in the obtained crosslinked resin particles (B-3) is 1.70 μm and the gel fraction is 95%.

[0190] 2-3. Raw materials for sheet or film molded body 2-3-1. Thermoplastic resin (A) (A-1): PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)): manufactured by Kaneka Corporation, Kaneka Biodegradable Polymer PHBH (registered trademark), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), repeating unit composition: (3-hydroxybutyrate) / (3-hydroxyhexanoate)=94.4 / 5.6 (mol / mol), weight average molecular weight Mw: 530,000, Tg 3°C (A-2): PLA: manufactured by Total Corbion PLA, LUMINY (registered trademark) LX975 (A-3): PBSA: manufactured by Mitsubishi Chemical Corporation, FD92PB 2-3-2. Crosslinked resin particles (B) Crosslinked resin particles (B-1) prepared in (Production Example 1) Crosslinked resin particles (B-2) prepared in (Production Example 2) Crosslinked resin particles (B-3) prepared in (Production Example 3) 2-3-3. Nucleating agent Pentaerythritol: NeuRizer P manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 2-3-4. Lubricant Behenic acid amide: BNT22H manufactured by Nippon Fine Chemical Industry Co., Ltd. Erucic acid amide: Neutron S manufactured by Nippon Fine Chemical Industry Co., Ltd.

[0191] 2-4. Method for producing sheet or film molded body (Examples 1 to 3 and Comparative Example 1) For each Example and Comparative Example, the thermoplastic resin (A), crosslinked resin particles (B), crystal nucleating agent, and lubricant listed in Table 1 were mixed in the amounts listed in Table 1 to obtain a mixture. The obtained mixture was melt-kneaded in a twin-screw extruder (KZW15TWIN-45WG, manufactured by Technovel Co., Ltd.) with the barrel temperature heated to 140°C to 165°C and the screw rotation speed at 80 rpm to obtain a melt-kneaded product (mixture). The obtained melt-kneaded product was dried in a dryer at 80°C for 4 hours to sufficiently reduce the moisture content, thereby obtaining a thermoplastic resin composition. Furthermore, the obtained thermoplastic resin composition was press-molded at 165°C to produce a sheet molded body and a film molded body. Furthermore, the obtained melt-kneaded product was molded (inflation molding) in an inflation molding machine (manufactured by AIKI Liotech Co., Ltd.) equipped with a Φ20 mm single-screw extruder (L / D 25) and a cylindrical die (die diameter 30 mm, die clearance 1.15 mm) under conditions of a screw rotation speed of 20 rpm, a temperature of 165°C, a film pulling speed of 2.0 m / min, and a folding width of 110 mm, to produce a cylindrical film molded product with a thickness of 40 μm.

[0192] (Examples 4 to 10) For each example and comparative example, the thermoplastic resin (A), crosslinked resin particles (B), crystal nucleating agent, and lubricant shown in Table 1 or 2 were mixed in the amounts shown in Table 1 or 2 to obtain a mixture. The obtained mixture was melt-kneaded in a twin-screw extruder (Shibaura Machine Co., Ltd. TEM-26SS) heated to a barrel temperature of 155°C at a screw rotation speed of 100 rpm to obtain a melt-kneaded product (mixture). The obtained melt-kneaded product was dried in a dehumidifying dryer at 50°C for 12 hours to sufficiently reduce the moisture content, thereby obtaining a thermoplastic resin composition. Furthermore, the obtained thermoplastic resin composition was press-molded at 120 to 165°C to produce a sheet molded product and a film molded product.

[0193] The sheet and film molded articles of each Example and Comparative Example were measured for tensile impact strength, Elmendorf tear strength, and puncture impact strength by the methods described above. The results are shown in Table 1.

[0194] Tables 1 and 2 show that Examples 1 to 10, in which crosslinked resin particles (B) were blended with thermoplastic resin (A), had higher Elmendorf tear strength and puncture impact strength values ​​than Comparative Example 1, which contained only thermoplastic resin (A). Furthermore, Tables 1 and 2 also show that Examples 1 to 10, in which crosslinked resin particles (B) were blended with thermoplastic resin (A), had higher tensile impact strength values ​​than Comparative Example 1, which contained only thermoplastic resin (A).

[0195] According to one embodiment of the present invention, a film or sheet molded article having excellent tear resistance and / or impact resistance can be provided, and therefore, this embodiment of the present invention can be suitably used in fields such as agriculture, fisheries, forestry, horticulture, medicine, hygiene products, the food industry, clothing, non-clothing, packaging, automobiles, building materials, and the like.

Claims

1. A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A), and 1 to 60 parts by weight of crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more (provided that the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight), the thermoplastic resin composition satisfying any one or more of the following (A) to (C): (A) The Elmendorf tear strength measured by the methods shown below in (A1) to (A4) is 3 N / mm or more: (A1) The thermoplastic resin composition is molded into a film having a thickness of 40 μm to obtain a film molded product; (A2) The film molded product obtained in (A1) is aged for 7 days under conditions of 23°C and 50% RH; (A3) The tear strength (unit: N) of the film molded body after aging is measured by a method in accordance with JIS K7128-2; (A4) The tear strength measured in (A3) is divided by the thickness (unit: mm) of the film molded body to calculate the Elmendorf tear strength; (B) The Elmendorf tear strength measured by the methods shown in (B1) to (B4) below is 3 N / mm or more: (B1) The thermoplastic resin composition is molded into a film having a thickness of 50 μm to 100 μm to obtain a film molded body; (B2) The film molded body obtained in (B1) is aged for 7 days under conditions of 23° C. and 50% RH; (B3) The tear strength (unit: N) of the film molded body after aging is measured by a method in accordance with JIS K7128-2; (B4) The tear strength measured in (B3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength; (C) The Elmendorf tear strength measured by the methods shown in (C1) to (C4) below is 5 N / mm or more: (C1) The thermoplastic resin composition is molded into a film having a thickness of more than 100 μm and not more than 120 μm to obtain a film molded article; (C2) The film molded article obtained in (C1) is aged for 7 days under conditions of 23° C. and 50% RH;(C3) The tear strength (unit: N) of the film molded article after aging is measured by a method in accordance with JIS K7128-2; (C4) The tear strength measured in (C3) is divided by the thickness (unit: mm) of the film molded article to calculate the Elmendorf tear strength; 2. A film or sheet molded product obtained by molding a thermoplastic resin composition, the thermoplastic resin composition comprising 40 to 99 parts by weight of a thermoplastic resin (A) and 1 to 60 parts by weight of crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more [wherein the total amount of the thermoplastic resin (A) and the crosslinked resin particles (B) is 100 parts by weight], the thermoplastic resin composition having an impact energy of 0.3 J or more at the maximum impact force point in a puncture impact test measured by the following methods (1) to (3): (1) The thermoplastic resin composition is molded into a sheet having a thickness of 900 μm to obtain a sheet molded product; (2) The sheet molded product obtained in step (1) is aged for 7 days under conditions of 23°C and 50% RH, and then cut into a shape of 60 mm x 60 mm; (3) The cut-out sheet molded product is subjected to ASTM The impact energy (J) at the maximum impact point is measured at a test temperature of 23° C. and a test speed of 3 m / sec using a method in accordance with D3763-15.

3. The film or sheet molded article according to claim 1 or 2, wherein the polyhydroxyalkanoate resin is a poly(3-hydroxyalkanoate) resin.

4. The film or sheet molding according to claim 1 or 2, wherein the crosslinked resin particles (B) have a volume average particle diameter of 0.10 μm to 10.00 μm.

5. The film or sheet molding according to claim 1 or 2, wherein the crosslinked resin particles (B) are crosslinked using a peroxide.

6. The film or sheet molding according to claim 5, wherein the crosslinked resin particles (B) are crosslinked in the presence of the peroxide and a polyfunctional compound.

7. The film or sheet molding according to claim 1 or 2, wherein the crosslinked resin particles (B) are not foamed.

8. A film or sheet molded product according to claim 1 or 2, wherein the thermoplastic resin (A) contains a biodegradable resin.

9. The film or sheet molded product according to claim 8, wherein the biodegradable resin includes a polyester-based resin.

10. The film or sheet molded product according to claim 1 or 2, further comprising a crystal nucleating agent and / or a lubricant.

11. The film or sheet molding according to claim 1 or 2, which is formed by inflation molding, extrusion molding, calendar molding, T-die extrusion molding, casting, rolling or pressing.