Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
  • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
  • A01G9/02—Receptacles, e.g. flower-pots or boxes; Glasses for cultivating flowers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
  • C08K5/1539—Cyclic anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

• thermoplastic resin composition for agricultural materials and agricultural materials.
• plastics are easy to mold and process, they are used in a wide range of fields, including electrical and electronic equipment parts, automobile parts, medical parts, and food containers, and are given physical properties or functionality, such as strength, depending on the application. In the agricultural materials field, they are used in applications that require water resistance and strength.
• Agricultural materials include, for example, mulch films used to raise or keep soil temperature warm and for the purpose of pest control, and seedling pots, a type of special container for growing seedlings.
• Patent Document 1 describes a mulch film that has enhanced biodegradability by containing a specific mass ratio of a biodegradable resin selected from polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and a basic filler such as calcium oxide, calcium hydroxide, and calcium carbonate.
• a biodegradable resin selected from polylactic acid, polybutylene succinate, and polybutylene succinate adipate
• a basic filler such as calcium oxide, calcium hydroxide, and calcium carbonate.
• Patent Document 2 describes a technology that further enhances biodegradability by including a specific mass ratio of a hardly hydrolyzable biodegradable resin such as polylactic acid, an ester decomposition promoter made of an easily hydrolyzable polymer, and an ester decomposition promoter made of inorganic particles that accelerate the hydrolysis of the ester decomposition promoter.
• a hardly hydrolyzable biodegradable resin such as polylactic acid
• an ester decomposition promoter made of an easily hydrolyzable polymer
• an ester decomposition promoter made of inorganic particles that accelerate the hydrolysis of the ester decomposition promoter.
• Basic fillers promote the biodegradability of molded products when buried in soil. However, because they accelerate hydrolysis during molding, they affect the moldability of the resin composition, causing molding defects such as uneven thickness in inflation molding applications such as agricultural mulch films. In particular, problems occur with molding poorly in deep-draw moldings with high stretch ratios such as seedling pots and plug trays.
• leafy vegetables such as green onions and chives have a short period from sowing to planting, and it is desirable for them to be buried in the soil and decompose within 1-2 months, so there is a demand for decomposition in an even shorter period than before.
• the present disclosure has been made in consideration of the above circumstances, and aims to provide a thermoplastic resin composition for agricultural materials that is capable of achieving both high biodegradability and moldability, and that can be used to produce even difficult deep-draw molded articles, and an agricultural material made from the thermoplastic resin composition for agricultural materials.
• thermoplastic resin composition for agricultural materials having the composition shown below, thereby completing the present invention.
• thermoplastic resin composition for agricultural materials comprising a basic filler (A), a biodegradable resin (B), and a thickener (C), wherein the basic filler (A) has a pH in water of 8.5 to 12.5, the biodegradable resin (B) comprises an aliphatic polyester resin (B1) and an aliphatic aromatic polyester resin (B2), and the thickener (C) comprises at least one selected from the group consisting of a carbodiimide compound, a cellulose fiber, an oxazoline compound, an acid anhydride compound, and a silica-based filler, and the content of the basic filler (A) is 5 to 30% by mass and the content of the thickener (C) is 0.5 to 3% by mass, based on 100% by mass of the thermoplastic resin composition.
• the basic filler (A) has a pH in water of 8.5 to 12.5
• the biodegradable resin (B) comprises an aliphatic polyester resin (B1) and an aliphatic aromatic polyester resin (B
• thermoplastic resin composition for agricultural materials according to ⁇ 1> wherein the basic filler (A) includes at least one selected from the group consisting of calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, and magnesium hydroxide.
• the basic filler (A) has a pH in water of 10.0 to 12.5.
• the thickener (C) contains at least one of a carbodiimide compound and a cellulose fiber.
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 5> wherein the content of the aliphatic polyester-based resin (B1) is 100 to 300 parts by mass per 100 parts by mass of the aliphatic-aromatic polyester-based resin (B2).
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 6> wherein the content of the aliphatic polyester-based resin (B1) is 130 to 300 parts by mass per 100 parts by mass of the aliphatic-aromatic polyester-based resin (B2).
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 7> having a melt viscosity at a shear rate of 243 s -1 of 1000 Pa s or more and less than 5000 Pa s at a temperature of not less than the melting point of the biodegradable resin (B) and not more than the melting point + 40°C.
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 8> which is used for blow molding or vacuum molding.
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 9> which is for use in seedling containers.
• ⁇ 11> An agricultural material formed using the thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 10> above.
• ⁇ 12> The agricultural material according to ⁇ 11>, which is a seedling container.
• ⁇ 13> The agricultural material according to ⁇ 11>, which is a seedling container in which seeds are raised before being buried in soil, and after the seedling raising period, the seedling container is buried in soil to cultivate plants.
• thermoplastic resin composition for agricultural materials that has biodegradability and good moldability, and an agricultural material made of the thermoplastic resin composition for agricultural materials. Furthermore, it is possible to produce even deep-drawn molded articles, which is highly difficult to produce, and it is possible to provide a thermoplastic resin composition for agricultural materials that exhibits high biodegradability, and agricultural materials made of the thermoplastic resin composition for agricultural materials.
• thermoplastic resin composition for agricultural materials may also be referred to as a "resin composition.”
• resin composition various components appearing in this specification may be used independently as a single type or as a mixture of two or more types.
• the numerical values specified in this specification are values determined by the methods disclosed in the embodiments or examples.
• the thermoplastic resin composition for agricultural materials is a thermoplastic resin composition comprising a basic filler (A), a biodegradable resin (B), and a thickener (C), wherein the basic filler (A) has a pH in water of 8.5 to 12.5, the biodegradable resin (B) comprises an aliphatic polyester-based resin (B1) and an aliphatic aromatic polyester-based resin (B2), and the thickener (C) comprises at least one selected from the group consisting of a carbodiimide compound, a cellulose fiber, an oxazoline compound, an epoxy compound, an acid anhydride compound, and a silica-based filler, Based on 100% by mass of the thermoplastic resin composition, the content of the basic filler (A) is 3 to 30% by mass, and the content of the thickener (C) is 0.01 to 3% by mass.
• a resin composition makes it possible to achieve both high biodegradability and moldability. Furthermore,
• the decomposition process of the resin composition mainly comprises two stages.
• the molecular weight of the resin constituting the agricultural material (such as seedling pot or mulch film) which is a molded product of the resin composition is reduced by hydrolysis or oxidative decomposition.
• the second stage microorganisms in the soil decompose the individual pieces of agricultural materials made of low molecular weight resin. Since the molecular weight of resins continues to decrease while agricultural materials are stored or used, it is important to control hydrolysis in the first stage.
• One factor in hydrolysis is the crystallinity of the resin. Hydrolysis is more likely to progress in the amorphous region than in the crystalline region, so it is possible to suppress hydrolysis by increasing the crystallinity.
• the particles act as crystal nuclei and promote the formation of crystals (nucleating effect), improving crystallinity and providing an effect of inhibiting hydrolysis.
• the thermoplastic resin composition for agricultural materials of this embodiment contains specific amounts of a specific basic filler (A) and a specific thickener (C), so that the biodegradation rate of the agricultural material made of the resin composition can be adjusted.
• A specific basic filler
• C specific thickener
• the basic filler (A) has a pH in water of 8.5 to 12.5 and has the function of promoting the hydrolysis of the biodegradable resin (B).
• the basic filler (A) is not particularly limited as long as it is a basic filler with a pH of 8.5 to 12.5 in water, and any commonly available basic filler can be used. When an agricultural material formed using the resin composition is buried in soil and becomes rich in moisture, the basic filler (A) can appropriately promote hydrolysis of the biodegradable resin (B) under basic conditions.
• Examples of the basic filler (A) include basic compounds containing alkali metals or alkaline earth metals, zeolites that release ions of alkali metals or alkaline earth metals, ion-releasing fillers, hydrotalcites, and the like.
• the use of these basic fillers (A) can promote hydrolysis, which is the first stage of the decomposition process of the resin composition, and reduce the molecular weight of the biodegradable resin (B), thereby enabling a rapid transition to the second stage, the decomposition process by microorganisms in the soil.
• the pH is preferably 9.0 to 11.0.
• the pH is more preferably 9.0 to 12.5, 10.0 to 12.5, 10.5 to 12.5, 11.0 to 12.5, or 12.0 to 12.5.
• the pH is more preferably 8.5 to 12.0, 8.5 to 11.0, 8.5 to 10.0, 8.5 to 9.5, or 8.5 to 9.0.
• the pH of the basic filler is a pH value measured with a pH meter at 23° C.
• a pH meter a PH meter HM-30P manufactured by Toa DKK Corporation or the like can be used.
• the pH can be measured using an aqueous solution
• the pH can be measured using the supernatant of the dispersion. Specifically, for example, 0.5 g of the basic filler is weighed out and placed in a plastic container, 50 ml of deionized water is added, and the container is shaken with a shaker for 30 minutes. Then, the container is centrifuged to separate the solid and liquid.
• the temperature of the supernatant water is stabilized in a thermostatic bath at 23° C., and the pH value measured with a pH meter (PH meter HM-30P, manufactured by Toa DKK Corporation) can be regarded as the pH of the basic filler.
• Basic compounds containing alkali metals or alkaline earth metals include carbonates, bicarbonates, silicates, phosphates, oxides, hydroxides, etc., such as sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, calcium silicate, magnesium silicate, sodium phosphate, calcium oxide, calcium hydroxide, magnesium hydroxide, etc.
• zeolites that release alkali metal or alkaline earth metal ions various natural or synthetic zeolites that contain alkali metal or alkaline earth metal ions as exchangeable ions can be used.
• Ion-releasing fillers include oxide glasses such as aluminosilicate glass, borosilicate glass, and soda-lime glass that contain alkali metals or alkaline earth metals, and fluoride glasses such as zirconium fluoride glass.
• a basic compound containing an alkali metal or an alkaline earth metal is preferred, a carbonate, oxide, or hydroxide containing an alkali metal or an alkaline earth metal is preferred, and calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, or magnesium hydroxide is even more preferred.
• carbonates such as calcium carbonate and magnesium carbonate are particularly preferred.
• the resin composition of the present disclosure can suppress the diffusion of excess base into the soil.
• the basic filler (A) may be used alone or in combination of two or more types.
• the average particle size of the basic filler (A) is preferably 1 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
• the average particle size of the basic filler (A) in the resin composition contributes to moldability, so it is preferable that the average particle size of the basic filler (A) be in the above-mentioned range.
• the average particle size of the basic filler (A) can be determined by a laser diffraction method.
• a laser diffraction method is used in which a dispersion of the dispersed basic filler (A) is irradiated with laser light, and the angular change in intensity of light scattered when the laser light passes through the solution is measured to obtain a particle size distribution, and the average particle size can be calculated as the median value at which the cumulative value on a volume basis becomes 50%.
• the particle size distribution meter that can be used is, for example, a particle size distribution meter Microtrack HRA manufactured by Nikkiso Co., Ltd.
• a measurement sample is prepared by dispersing the basic filler (A) in isopropyl alcohol.
• the content of the basic filler (A) is preferably 3 to 30% by mass. This content may be 3% by mass or more, 4% by mass or more, 5% by mass or more, 8% by mass or more, or 10% by mass or more. This content may be within these lower limit values and may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 18% by mass or less, or 15% by mass or less.
• the pH of the basic filler (A) in water is 8.5 to 12.5, so when the agricultural material is buried in soil and becomes rich in moisture, an appropriate basic environment is created, which can promote hydrolysis of the biodegradable resin (B).
• Biodegradable resin (B) The biodegradable resin (B) is decomposed by the action of various microorganisms present in soil or water.
• the resin composition of the present disclosure contains, as the biodegradable resin (B), an aliphatic polyester-based
• the present invention relates to a resin composition having excellent biodegradability and moldability, and more particularly to a resin composition having excellent biodegradability and moldability.
• the biodegradable resin (B) may further be any biodegradable resin that is generally available. These biodegradable resins may be used alone or in combination of two or more. Good too.
• the content of the aliphatic polyester resin (B1) is preferably equal to or greater than the content of the aliphatic aromatic polyester resin (B2).
• the content of the aliphatic polyester resin (B1) relative to 100 parts by mass of the aliphatic aromatic polyester resin (B2) is preferably 100 parts by mass or more, more preferably 110% by mass or more, 120 parts by mass or more, 130 parts by mass or more, or 140 parts by mass or more, and from the viewpoint of enhancing biodegradability, it is even more preferable that it is 150 parts by mass or more. Also, it is preferably 300 parts by mass or less, more preferably 280 parts by mass or less, 250 parts by mass or less, 230 parts by mass or less, or 200 parts by mass or less, and from the viewpoint of enhancing moldability, it is even more preferable that it is 150 parts by mass or less.
• the content of the aliphatic polyester resin (B1) relative to 100 parts by mass of this aliphatic aromatic polyester resin (B2) may be 100 to 300 parts by mass, 110 to 280 parts by mass, 120 to 250 parts by mass, 130 to 230 parts by mass, or 140 to 200 parts by mass.
• aliphatic polyester resin (B1) examples include aliphatic polyesters obtained by polycondensation reaction of aliphatic diols and aliphatic dicarboxylic acids, and polylactic acids obtained by polycondensation of lactic acid.
• aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in mixtures.
• 1,4-butanediol examples include 1,4-butanediol.
• the aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides that are derivatives of these may also be used.
• succinic acid or succinic anhydride, or a mixture of these with adipic acid is preferable.
• PBS polybutylene succinate
• PBSA polybutylene succinate adipate
• PLA polylactic acid
• REVODE trade name
• the aliphatic polyester resin (B1) contains the aliphatic polyester obtained by the polycondensation reaction of an aliphatic diol and an aliphatic dicarboxylic acid in the maximum amount among all components.
• the aliphatic polyester obtained by the polycondensation reaction of an aliphatic diol and an aliphatic dicarboxylic acid is contained in an amount of 20 mass% or more, 50 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, or 100 mass% based on 100 mass% of the aliphatic polyester resin (B1).
• the aliphatic polyester is a copolymer consisting of units derived from an aliphatic diol and units derived from an aliphatic dicarboxylic acid.
• aliphatic aromatic polyester resin (B2) examples include copolymers containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and/or alicyclic diol unit.
• the diol component that gives the diol unit usually has 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.
• diols having 2 to 4 carbon atoms are preferred, with ethylene glycol and 1,4-butanediol being more preferred, and 1,4-butanediol being even more preferred.
• the dicarboxylic acid component that gives the dicarboxylic acid unit usually has 2 to 10 carbon atoms, such as succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Among these, succinic acid or adipic acid is preferred.
• aromatic dicarboxylic acid components that give aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
• terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.
• the polymer include polybutylene adipate terephthalate (PBAT) (for example, "Ecoflex” (trade name) manufactured by BASF Co., Ltd.), which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid.
• PBAT polybutylene adipate terephthalate
• the biodegradable resin (B) may be a combination of the aliphatic polyester resin (B1) and the aliphatic aromatic polyester resin (B2) with other biodegradable resins.
• the aliphatic polyester resin (B1) in addition to the above examples, for example, poly(3-hydroxyalkanoate) (particularly poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (for example, "Aonilex" (product name) manufactured by Kaneka Corporation), polycaprolactone, etc. may also be used.
• the content of the biodegradable resin (B) may be 35 to 95% by mass, more preferably 35 to 94.99% by mass, even more preferably 35 to 94.5% by mass, and even more preferably 39 to 90% by mass, based on the resin composition (100% by mass).
• the content of the biodegradable resin (B) within the above range is preferable because it allows the resin composition to have both good processability and moldability.
• the total content of the aliphatic polyester resin (B1) and the aliphatic aromatic polyester resin (B2) may be 100% by mass, preferably 80% by mass or more, and more preferably 90% by mass or more.
• the thickener (C) is a viscosity modifier that adjusts the viscosity of the resin composition to improve moldability, and has the function of increasing the melt tension of the resin composition, which is an index of moldability.
• the thickener (C) includes at least one selected from the group consisting of carbodiimide compounds, oxazoline compounds, acid anhydride compounds, cellulose fibers, and silica-based fillers.
• the thickener (C) may additionally include an epoxy compound. Since the epoxy compound may act as a compatibilizer for the polyester resin, it is preferable to limit its use in order to obtain the strength of the agricultural material. Alternatively, the epoxy compound may be used in combination with another thickener (C).
• the thickener (C) When the thickener (C) is a polyfunctional compound, it can form a crosslinked structure with the biodegradable resin (B) to increase the melt tension of the resin composition.
• polyfunctional compounds include polyfunctional carbodiimide compounds, polyfunctional oxazoline compounds, epoxy compounds, and acid anhydride compounds.
• the polyfunctional carbodiimide compound may be a monomer or polymer having two or more carbodiimide groups, but a polymer having two or more carbodiimide groups is preferred.
• a reactive group can be introduced into the biodegradable resin (B) to form a crosslinked structure starting from this reactive group, thereby increasing the melt tension of the resin composition.
• reactive compounds include carbodiimide compounds, oxazoline compounds, epoxy compounds, and acid anhydride compounds. It is preferable to use a cyclic carbodiimide as the carbodiimide compound.
• a cyclic carbodiimide compound is a compound having a carbodiimide group on an aliphatic ring or an aromatic ring.
• the melt tension of the resin composition can be increased by increasing the solid content of the resin composition and thickening the resin composition.
• the filler may be either an organic filler or an inorganic filler, and examples of the filler include cellulose fiber and silica-based filler.
• CMF cellulose microfiber
• CDI carbodiimide compound
• Cellulose microfiber refers to relatively large cellulose fibers obtained by treating pulp with hot water or the like, hydrolyzing and weakening it, and then reducing the number of defibration steps in the cellulose that has been defibrated by a pulverization method such as a high-pressure homogenizer.
• a pulverization method such as a high-pressure homogenizer.
• the strength of the resin composition is increased due to the filler effect of the cellulose microfiber.
• the silica-based filler has a filler effect similar to that of the cellulose microfiber, and therefore increases the strength of the resin composition in the same way as the cellulose microfiber.
• blow molding can be used to mold a resin composition that contains at least one of cellulose microfiber and silica-based filler as the thickener (C).
• a carbodiimide compound When a carbodiimide compound is contained in a resin composition, the resin reacts with the carbodiimide compound, increasing the molecular weight of the resin, and it takes time for the resin to be hydrolyzed to reduce its molecular weight, slowing down the biodegradation rate. For this reason, in the case of agricultural materials that require a strong resin composition, it is preferable to contain a carbodiimide compound as a thickener (C).
• oxazoline compounds, epoxy compounds, and acid anhydride compounds each have reactivity with resins like carbodiimide compounds, so these compounds can also improve the strength of the resin composition.
• a resin composition containing at least one of a carbodiimide compound, an oxazoline compound, an epoxy compound, and an acid anhydride compound can be molded, for example, using vacuum molding.
• carbodiimide compound examples include polycarbodiimide compounds such as "Carbodilite HMV-15CA (trade name)” manufactured by Nisshinbo Chemical Co., Ltd.; monocarbodiimides such as dicyclohexylcarbodiimide, diphenylcarbodiimide, di- ⁇ -naphthylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, and di-t-butylcarbodiimide; and cyclic carbodiimide compounds such as "Carbodista TCC-NP” (trade name) manufactured by Teijin Limited. These compounds may be used alone or in combination of two or more kinds.
• An example of the cellulose fiber is "C-1: KC Flock W-50" (product name) manufactured by Nippon Paper Industries Co., Ltd.
• Examples of the oxazoline compound include “EPOCROS RA-45” (trade name) and “EPOCROS RPS-1005" (trade name) manufactured by Nippon Shokubai Co., Ltd. These compounds may be used alone or in combination of two or more kinds.
• Examples of the epoxy compound include epoxy-acrylic compounds ("Joncryl ADR-4468" (product name) and “Joncryl ADR-4400” (product name) manufactured by BASF Corporation, "Arphon UG-4040" (product name) manufactured by Toagosei Co., Ltd., and “Arphon UG-4070” (product name) manufactured by Toagosei Co., Ltd.). These compounds may be used alone or in combination of two or more kinds.
• Examples of the acid anhydride compound include styrene-maleic anhydride compound (PALMER).
• PALMER styrene-maleic anhydride compound
• Examples of such products include "XIBOND120" (product name), "XIBOND140” (product name), “XIBOND160” (product name), “XIBOND180” (product name), “XIBOND200” (product name), “XIBOND220” (product name), “XIBOND250” (product name), and “XIBOND280” (product name) manufactured by Holland Corporation, and "XIRAN1000" (product name), "XIRAN2000” (product name), "XIRAN2500” (product name), "XIRAN3000” (product name), “XIRAN4000” (product name), “XIRAN6000” (product name), “XIRAN9000” (product name), “XIRAN3500” (product name), and “XIRAN3600” (product name) manufactured by Tomoe Engineering Co., Ltd
• silica-based fillers examples include silica fillers (manufactured by Nippon Aerosil Co., Ltd., such as "Aerosil 130" (trade name), “Aerosil 150” (trade name), “Aerosil 200” (trade name), “Aerosil 300” (trade name), “Aerosil RX200” (trade name), and “Aerosil RY200” (trade name), and manufactured by Tosoh Silica Corporation, such as “Nipseal SS-50" (trade name), “Nipseal SS-50B” (trade name), “Nipseal SS-50F” (trade name), “Nipseal K-500” (trade name), and “Nipseal G-300” (trade name). These may be used alone or in combination of two or more types.
• the content of the thickener (C) is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, and may be 0.01 to 1 part by mass, or 0.1 to 0.8 parts by mass, per 100 parts by mass of the resin composition in order to provide an appropriate viscosity for the resin composition.
• the content of the thickener (C) may be 0.01 to 3 parts by mass, 0.01 to 2.5 parts by mass, 0.01 to 2 parts by mass, 0.01 to 1.5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.5 parts by mass in 100 parts by mass of the resin composition.
• the content of the thickener (C) may be 0.01 to 3 parts by mass, 0.1 to 3 parts by mass, 0.2 to 3 parts by mass, 0.3 to 3 parts by mass, 0.5 to 3 parts by mass, 1 to 3 parts by mass, or 2 to 3 parts by mass in 100 parts by mass of the resin composition. If this content is 0.5 parts by mass or more, deep drawing molding is also possible using blow molding and vacuum molding. Furthermore, if this content is in the range of 1.5 parts by mass or more, moldability is further improved, and even when vacuum molding is used, poor appearance and strength reduction can be suppressed.
• the content of the basic filler (A) may be 8 to 25 mass % or 10 to 20 mass % and the content of the thickener (C) may be 0.5 to 3 mass % based on 100 mass % of the thermoplastic resin composition. More preferably, the content of the basic filler (A) may be 5 to 30 mass % and the content of the thickener (C) may be 1 to 3 parts by mass or 2 to 3 parts by mass based on 100 mass % of the thermoplastic resin composition.
• the resin composition may contain starch.
• starch is preferred because it promotes the second step of decomposition by microorganisms in the soil, thereby providing an additional promotion effect.
• Starch (D) promotes the activity (biodegradability) of various microorganisms present in soil or water.
• Starch (D) is not particularly limited, and commonly available starch can be used. Examples include corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, etc.
• corn starch having a uniform particle size of about 20 ⁇ m is preferably used because it can make the thickness of the agricultural material made of the resin composition uniform (reduce surface unevenness), suppress the occurrence of thin parts, and as a result, suppress damage to the agricultural material.
• These may be used alone or in combination of two or more.
• the content of starch (D) is a component that can adjust the biodegradation rate, and the content is preferably 5 to 60 mass% in 100 mass% of the resin composition, and may be 10 to 50 mass%, 10 to 40 mass%, or 10 to 30 mass%.
• the content of starch (D) is 5 mass% or more, biodegradation is promoted, and when it is 60 mass% or less, the content of biodegradable resin (B) is secured and moldability can be guaranteed.
• the content of basic filler (A) and thickener (C) by specifying the content of basic filler (A) and thickener (C), the hydrolysis of biodegradable resin (B) in soil is promoted, so that the rate of biodegradation in soil is increased and the moldability of the resin composition can also be improved. Therefore, in some embodiments, the biodegradability of agricultural materials can be obtained regardless of the biodegradation promotion effect of starch (D).
• the content of starch (D) may be 0-20% by mass, 0-15% by mass, 0-10% by mass, or 0-5% by mass, based on 100% by mass of the resin composition, and starch (D) may not be substantially contained in the resin composition.
• the average particle size of starch (D) is preferably 5 to 50 ⁇ m, and may be 10 to 50 ⁇ m.
• the average particle size of starch (D) can be calculated, for example, by observing the particles of starch (A) under a scanning electron microscope, randomly observing 100 particles, measuring the distance between the two most distant points on the outline of each particle based on the length of a micron marker on the screen, and averaging the results.
• the mass ratio of the starch (D) to the basic filler (A), basic filler (A)/starch (D), is preferably 80/20 to 20/80, and more preferably 50/50 to 25/75. This is preferable because it has a further promoting effect and can provide agricultural materials with better biodegradability.
• the resin composition may optionally contain other components such as additives as necessary.
• additives include dispersants, lubricants (higher fatty acid metal salts, waxes, etc.), surfactants, antistatic agents, flame retardants, antioxidants, UV absorbers, fillers, pigments, etc.
• the selection of other optional components and the amount of use thereof are not particularly limited as long as they are within a range that can solve the problem of one embodiment of the present invention.
• a combination of multiple additives may be used.
• the resin composition may partially contain a resin other than the biodegradable resin within a range that does not inhibit the effect of one embodiment of the present invention.
• the resin composition contains a biodegradable resin (B), but does not need to contain a plasticizer from the viewpoint of adjusting the rate of biodegradation.
• a plasticizer By not containing a plasticizer, the progress of biodegradation can be further suppressed in agricultural materials formed using the resin composition before they are buried in the soil.
• the moldability of the resin composition can also be improved.
• the amount of plasticizer per 100 parts by mass of biodegradable resin (B) may be 5 parts by mass or less, 1 part by mass or less, or 0.1 parts by mass or less.
• the resin composition By coloring the resin composition with a pigment, it is possible to produce molded products with excellent heat-shielding properties or easily identifiable molded products.
• a pigment There are no particular limitations on the pigment, and any commonly available pigment can be used, but from the perspective of the natural environment, it is preferable that the pigment does not substantially contain pigments containing cadmium, lead, chromium, arsenic, mercury, copper, selenium, nickel, molybdenum, or fluorine.
• the resin composition contains a pigment
• a dispersant for dispersing the pigment is a fatty acid metal salt.
• the fatty acid component of the fatty acid metal salt is preferably a chain carboxylic acid having 6 to 30 carbon atoms, which may be linear or branched, and may have only saturated bonds or unsaturated bonds.
• fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, and montanic acid.
• the metal is preferably an element of Group 1, Group 2, Group 12, or Group 13, and more preferably an element of Group 1 or Group 2. Specific examples include sodium, potassium, calcium, magnesium, and barium.
• fatty acid metal salts examples include calcium stearate, magnesium stearate, barium stearate, calcium laurate, magnesium laurate, sodium montanate, etc. These may be used alone or in combination of two or more. Of these, calcium stearate, magnesium stearate, calcium laurate, and magnesium laurate are preferred.
• the processability during extrusion is such that strand breakage occurs 5 times or less during continuous production for 1 hour, and may occur 1 to 5 times, and it is preferable that strand breakage does not occur.
• melt Viscosity In the above-mentioned thermoplastic resin composition for agricultural materials, the melt viscosity at a shear rate of 243 s -1 according to JIS K7199:1999 is, from the viewpoint of the strength of the obtained molded article and the fluidity and moldability of the resin composition, preferably 1000 Pa ⁇ s or more and less than 5000 Pa ⁇ s, and more preferably 1500 Pa ⁇ s or more and less than 4500 Pa ⁇ s, at a temperature of not less than the melting point of the biodegradable resin (B) and not more than the melting point + 40°C.
• thermoplastic resin composition for agricultural materials can be used for various agricultural materials.
• this resin composition can be suitably used for seedling containers.
• a seedling container is a container used to grow seedlings in a container until they grow to a certain extent, rather than sowing the seeds directly in a field. Since a molded product using the resin composition of this embodiment is appropriately biodegradable in soil, there is no need to remove the seedlings from the seedling container after they have grown and transplant them, and they can be transplanted into soil in the seedling container as they are.
• seedling containers include seedling pots and plug trays.
• the resin composition of this embodiment can be produced by kneading the basic filler (A) and the thickener (C) at a temperature at which the biodegradable resin (B) melts.
• the biodegradable resin (B), the basic filler (A), the thickener (C), and various additives are added as necessary, and mixed and melt-kneaded with a batch kneader such as a kneader, a roll mill, a super mixer, a high-speed mixer, a ball mill, a sand mill, an attritor, or a Banbury mixer, a single-screw extruder, a twin-screw extruder, a rotor-type twin-screw kneader, or the like to form a pellet-shaped, powder-shaped, granular, or bead-shaped resin composition. It is preferable to form the pellets with a single-screw extruder
• the resin composition may be used in the form of either a master batch or a compound.
• the agricultural material can be produced by mixing the masterbatch with, for example, the same biodegradable resin (B) as that used in the production of the masterbatch as a diluent resin, which is the main resin of the agricultural material.
• the content of the masterbatch is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass, of the masterbatch per 100 parts by mass of the biodegradable resin (B) which is the main resin.
• the biodegradable resin (B) used as the diluting resin may be the same as or different from that used in the production of the master batch, but it is preferable to use the same biodegradable resin because this provides excellent compatibility between the thermoplastic resin composition and the resin.
• the compound after the compound is produced, the compound can be used as it is to produce agricultural materials by the above-mentioned method.
• the agricultural material of the present embodiment can be obtained by molding the above-mentioned thermoplastic resin composition for agricultural materials.
• the agricultural material include seedling containers such as seedling pots and plug trays, mulch films, containers, and agricultural nets.
• the agricultural material of this embodiment makes it possible to achieve both biodegradability and formability even in the case of a deep-drawn molded product with a high stretch ratio, such as a seedling pot or plug tray.
• the deep-drawn molded product referred to here is a molded product whose depth is longer than its width.
• the agricultural material of this embodiment is preferably a seedling container in which seeds are raised before being buried in soil, and after the seedling raising period, the seedling container is buried in soil to cultivate plants.
• the seedling pot is a container used for the above-mentioned purpose.
• the method of molding the seedling pot is not particularly limited, but suitable methods include, for example, blow molding in which a heated and plasticized resin composition is extruded and directly placed in a mold without cooling and solidifying it, and air is blown into the mold, and vacuum molding in which a sheet or film of a heated and plasticized resin composition is placed on a mold and vacuum-suctioned from the inside of the mold to mold the pot.
• the seedling pot made of the above-mentioned resin composition biodegrades after being buried in soil, so it does not harm the natural environment and reduces the effort required to remove seedlings from the seedling pot and sow them.
• the seedling pot grows well without decomposing during the seedling growth period of about 2-4 months before being buried in soil.
• the seedling pot has a strength suitable for seedling growth purposes, making it easy to handle and able to maintain an appropriate shape during the seedling growth period.
• a mulch film is a film that covers the base of a crop.
• the method for forming a film from the above-mentioned resin composition is not particularly limited, but suitable methods include extrusion molding in which a film extruded from a T-die using an extruder is cooled and solidified with a cast roll, or a method of forming using an inflation molding machine.
• the above-mentioned resin composition has an increased melt tension due to the thickener (C), and therefore drawdown (the phenomenon in which a preformed resin cannot withstand its own weight and sags in the direction of gravity) can be suppressed.
• the resin composition of this embodiment can be blow molded.
• the difference in weight between each seedling pot in the first set and each seedling pot in the third set can be made less than 30% of the weight of each seedling pot in the first set.
• the weight of each seedling pot may be 0.7 g or more and less than 0.8 g, preferably 0.8 g or more and less than 0.9 g, and more preferably 0.9 g or more. Blow moldability can be obtained by using the above-mentioned resin composition.
• the molded product is a seedling pot
• the occurrence of defective appearances due to sagging such as wrinkles caused by bending of the sheet can be suppressed.
• the resin composition it is sufficient as long as vacuum molding can be performed using the resin composition, and it is preferable if there are only a few defective appearances, and it is even more preferable if there are no defective appearances.
• the brittleness of the seedling pot is such that when 1 kg of soil is placed in the seedling pot and it is dropped from a height of 5 m, 3 or less of 10 seedling pots break, 1 to 3 or less of 10 seedling pots may break, and it is preferable that none of the pots break.
• Biodegradation rate When a molded article made from the above-mentioned resin composition is buried in the ground for six months, it is sufficient that the molded article is decomposed and has holes in places, and it is preferable that the molded article is decomposed and falls apart. By using the above-mentioned resin composition, a molded article with an appropriately adjusted biodegradation rate can be obtained.
• thermoplastic resin composition for agricultural materials contains specific amounts of a basic filler (A) that promotes biodegradability and a thickener (C) that increases melt tension, making it possible to obtain agricultural materials with excellent biodegradability and moldability.
• A basic filler
• C thickener
• thermoplastic resin composition comprising a basic filler (A), a biodegradable resin (B), and a thickener (C),
• the basic filler (A) has a pH in water of 8.5 to 12.5;
• the biodegradable resin (B) includes an aliphatic polyester-based resin (B1) and an aliphatic aromatic polyester-based resin (B2),
• the thickener (C) includes at least one selected from the group consisting of a carbodiimide compound, a cellulose fiber, an oxazoline compound, an epoxy compound, an acid anhydride compound, and a silica-based filler, and preferably includes at least one selected from the group consisting of a carbodiimide compound, a cellulose fiber, an oxazoline compound, an acid anhydride compound, and a silica-based filler,
• a thermoplastic resin composition for agricultural materials comprising, based on 100% by
• the thickener (C) may contain at least one of a carbodiimide compound and cellulose fiber.
• the content of the aliphatic polyester resin (B1) may be 100 to 300 parts by mass, preferably 130 to 300 parts by mass, per 100 parts by mass of the aliphatic aromatic polyester resin (B2).
• ⁇ pH measurement> 0.5 g of the basic filler was weighed out and placed in a plastic container, 50 ml of deionized water was added, and the container was shaken for 30 minutes using a shaker. Then, the container was centrifuged to separate the solid and liquid. The temperature of the supernatant water was stabilized in a thermostatic bath at 23° C., and the pH was measured using a pH meter (PH meter HM-30P, manufactured by Toa DKK Corporation).
• the average particle diameters of the basic filler (A) and starch (D) are measured by the following method.
• Method for measuring average particle size of basic filler (A)> A sample was prepared by dispersing a basic filler in isopropyl alcohol. The obtained dispersion was irradiated with laser light using a particle size distribution meter Microtrack HRA manufactured by Nikkiso Co., Ltd., and the distribution pattern of the intensity of the light scattered when the laser light passes through the dispersion was measured to obtain a particle size distribution. Furthermore, the median diameter (50% diameter) on a volume basis was calculated from the particle size distribution value, and this was used as the average particle diameter.
• A-1 KS-1300 (calcium carbonate, manufactured by Calfine Co., Ltd., pH 9.0, average particle size: 1.8 ⁇ m)
• A-2 KS-500 (calcium carbonate, manufactured by Calfine Co., Ltd., pH 9.0, average particle size: 4.4 ⁇ m)
• A-3 KS-300 (calcium carbonate, manufactured by Calfine Co., Ltd., pH 9.0, average particle size: 8.9 ⁇ m)
• A-4 Magnesium carbonate (Kinsei) (Konoshima Chemical Co., Ltd., pH 10.0, average particle size: 10 ⁇ m)
• A-5 F-Lime-1300K (calcium oxide, manufactured by Calfine Co., Ltd., pH 12.4, average particle size: 5.0 ⁇ m)
• A-6 M-300 (calcium hydroxide, manufactured by Inoue Mitsukichi Shoten Co., Ltd., pH 12.4, average particle size: 5.0 ⁇ m)
• C-1 KC Flock W-50 (manufactured by Nippon Paper Industries Co., Ltd., cellulose microfiber, average fiber length: 50 ⁇ m)
• C-2 Carbodilite HMV-15CA (manufactured by Nisshinbo Chemical Co., Ltd., polycarbodiimide compound)
• C-3 Carbodista TCC-NP (manufactured by Teijin Limited, cyclic carbodiimide compound)
• C-4 Joncryl ADR-4468 (manufactured by BASF, epoxy-acrylic compound)
• C-5 XIBOND220 (styrene maleic anhydride compound, manufactured by PALMER HOLLAND)
• C-6 EPOCROS RA-45 (manufactured by Nippon Shokubai Co., Ltd., oxazoline compound)
• C-7 Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd., silica filler)
• C-8 Nips
• thermoplastic resin composition (compound) for agricultural materials) 5 parts by mass of (A-1) as a basic filler (A), 64.5 parts by mass of (B1-1) and 30 parts by mass of (B2-1) as a biodegradable resin (B), and 0.5 parts by mass of (C-1) as a thickener (C) were mixed, extruded at 190°C using a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.), and granulated to obtain a thermoplastic resin composition for agricultural materials.
• thermoplastic resin composition for agricultural materials was molded by blow molding and vacuum molding to obtain a seedling pot.
• thermoplastic resin compositions for agricultural materials and seedling pots were obtained in the same manner as in Example 1, except that the materials and the amounts (parts by mass) were changed to those shown in Table 1.
• thermoplastic resin compositions for agricultural materials of Comparative Examples 3, 4, and 7 to 9 had poor moldability and could not be used to manufacture seedling pots, so it was not possible to evaluate the strength, brittleness, and biodegradability rate of the molded products.
• thermoplastic resin compositions for agricultural materials and the seedling pots obtained in the Examples, Reference Examples, and Comparative Examples were evaluated according to the following criteria. The evaluation results are shown in Table 1.
• thermoplastic resin composition for agricultural materials during extrusion was evaluated.
• the evaluation criteria were as follows, with ⁇ and ⁇ being practical. [Evaluation Criteria] ⁇ : No strand breakage occurs during continuous production for 1 hour. ⁇ : Strand breakage occurs 1 to 5 times during continuous production for 1 hour. ⁇ : Strand breakage occurs six or more times during continuous production for one hour.
• ⁇ Blow moldability evaluation> Three sets of two seedling pots (diameter 9 cm, height 7 cm) were made in succession at 150°C using a direct blow molding machine (manufactured by Nippon Placon Co., Ltd.), and the difference between the weight of each seedling pot in the first set and the weight of each seedling pot in the third set (weight difference) and the weight of each seedling pot were evaluated as moldability during production.
• "blow molding is possible” means that the weight difference is less than 30% of the weight of each seedling pot in the first set.
• the evaluation criteria are as follows, with ⁇ and ⁇ being practical. [Evaluation Criteria] ⁇ : Blow molding is possible, and the weight of each seedling pot is 0.9 g or more. ⁇ : Blow molding is possible, and the weight of each seedling pot is 0.7 to less than 0.9 g. ⁇ : Blow molding is not possible.
• ⁇ Vacuum formability evaluation> A sheet measuring 30 cm long x 30 cm wide x 0.45 mm thick was molded at 180°C using a T-die molding machine. The molded sheet was heated to 110°C and molded into a seedling pot (diameter 6 cm, height 7 cm) using a vacuum molding machine, and the moldability during production was evaluated. The evaluation criteria were as follows, with ⁇ and ⁇ being practical. [Evaluation Criteria] ⁇ : Vacuum molding was possible, and the seedling pot had no defective appearance due to dripping. ⁇ : Vacuum molding was possible, but some defective parts in appearance due to dripping were observed in the seedling pot. ⁇ : Vacuum forming is not possible.
• ⁇ Biodegradation rate evaluation> The seedling pots prepared for the evaluation of blow moldability were filled with 1 kg of soil, and the shape of the seedling pots was checked after 4 months to evaluate biodegradability.
• the evaluation criteria were as follows, with ⁇ and ⁇ being considered practical. [Evaluation Criteria] ⁇ : The seedling pot retains its original shape. ⁇ : The seedling pot has decomposed and has holes in places. ⁇ : The seedling pot has decomposed and fallen into pieces. -: Seedling pots could not be made, and evaluation was not possible.

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