Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
• • 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
  • A01G9/029—Receptacles for seedlings
  • A01G9/0291—Planting receptacles specially adapted for remaining in the soil after planting
• • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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
  • C08K5/32—Compounds containing nitrogen bound to oxygen
• • 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
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/353—Five-membered rings
• • 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
• • 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
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
  • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/06—Biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/16—Fibres; Fibrils

Definitions

• the present invention relates to a thermoplastic resin composition for agricultural materials and agricultural materials.
• Plastic is easy to mold, it is used in a wide range of fields such as electrical and electronic equipment parts, automobile parts, medical parts, and food containers.
• Plastic molded products can be modified to improve physical properties such as strength or functionality depending on the application. is granted to. In the field of agricultural materials, it is used in applications that require water resistance and strength.
• Agricultural materials include, for example, mulch films used to raise or retain soil temperature and control pests, and seedling pots, which are a type of container dedicated to growing seeds and seedlings.
• Patent Document 1 describes that by containing aliphatic polyester resin, aromatic aliphatic polyester resin, starch, and polyhydric alcohol in a specific mass ratio, tear strength is strong, biodegradability, moldability, heat shrinkability, A film is described that has good transparency, a high modulus of elasticity, and is resistant to wrinkling.
• the film uses aliphatic polyester resin and aromatic aliphatic polyester resin as biodegradable materials, and by adjusting the content of polyhydric alcohol, it improves tear strength and tensile elasticity while promoting starch plasticization. This improves the physical properties of the resin composition, such as the
• the resin composition can be modified by adding a plasticizer such as a polyhydric alcohol, but if a plasticizer is included in the resin composition, , the surface of the resulting molded product becomes sticky, and the peelability between the resin composition and the mold of the molding machine during molding decreases, as well as the slipperiness to separate the molded products individually, which affects the molding of the resin composition.
• a plasticizer such as a polyhydric alcohol
• the present invention has been made in view of the above circumstances, and provides a heating material for agricultural materials that can produce molded products with suppressed surface stickiness, is biodegradable, and has good moldability.
• the object of the present invention is to provide a plastic resin composition and an agricultural material comprising the thermoplastic resin composition for agricultural materials.
• thermoplastic resin composition for agricultural materials having the structure shown below, and completed the present invention.
• thermoplastic resin composition for agricultural materials containing starch, a biodegradable resin, and a viscosity modifier, wherein the content of the plasticizer is in 100 parts by mass of the thermoplastic resin composition for agricultural materials.
• the biodegradable resin includes an aliphatic polyester resin and an aliphatic aromatic polyester resin, and the total amount of the aliphatic polyester resin and the aliphatic aromatic polyester resin is
• the content of the starch is 80 parts by mass or more in 100 parts by mass of the biodegradable resin, the content of the starch is 5 to 60 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials, and the biodegradable
• the content of the resin is 35 to 94.5 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials
• the viscosity modifier has a viscosity that increases the melt tension of the thermoplastic resin composition for agricultural materials.
• the viscosity modifier includes at least one selected from the group consisting of a carbodiimide compound, an oxazoline compound, an epoxy compound, an acid anhydride compound, a cellulose fiber, and a silica filler, and the viscosity modifier
• the content is 0.01 to 3 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials, and the content of the cellulose fiber is 0 parts by mass or more in 100 parts by mass of the thermoplastic resin composition for agricultural materials.
• a thermoplastic resin composition for agricultural materials wherein the content of the aliphatic polyester resin is less than 1.5 parts by mass, and the content of the aliphatic aromatic polyester resin is greater than or equal to the content of the aliphatic aromatic polyester resin.
• thermoplastic resin composition for agricultural materials according to ⁇ 1> wherein the content of the starch is 10 to 30 parts by mass based on 100 parts by mass of the thermoplastic resin composition for agricultural materials.
• ⁇ 5> The agriculture according to any one of ⁇ 1> to ⁇ 4>, wherein the content ratio (parts by mass) of the aliphatic polyester resin and the aliphatic aromatic polyester resin is 1 to 3:1.
• the melt viscosity at a shear rate of 243 s -1 is 1000 Pa ⁇ s or more and less than 5000 Pa ⁇ s at a temperature higher than the melting point of the biodegradable resin (B) and lower than the melting point +40°C, ⁇ 1> to ⁇ 5>
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 6> which is used for blow molding or vacuum forming.
• thermoplastic resin composition for agricultural materials according to any one of ⁇ 1> to ⁇ 7> which is for use in pots for raising seedlings.
• ⁇ 10> The agricultural material according to ⁇ 9>, which is a seedling-raising pot.
• thermoplastic resin composition for agricultural materials that can produce molded products with suppressed surface stickiness, has biodegradability, and has good moldability, and the agricultural materials Agricultural materials made of thermoplastic resin compositions can be provided.
• thermoplastic resin composition for agricultural materials is characterized in that it contains starch, a biodegradable resin, and a viscosity modifier, and does not contain a plasticizer.
• the resulting resin composition has good moldability, is biodegradable, and has a low surface area on the surface of the molded product. Stickiness can be suppressed.
• thermoplastic resin composition for agricultural materials is also referred to as “resin composition”
• starch is also referred to as “starch (A)
• biodegradable resin is also referred to as “biodegradable resin (B )
• viscosity modifier may also be described as “viscosity modifier (C)”
• plasticizer may also be described as “plasticizer (D)”.
• the decomposition process of the resin composition can be roughly divided into two.
• the molecular weight of the resin constituting the agricultural material seedling pot, mulch film, etc.
• the second step microorganisms in the soil decompose individual pieces of agricultural materials made of low-molecular-weight resin. Since the molecular weight of the resin continues to decrease while agricultural materials are stored or used, it is important to control hydrolysis in the first stage.
• the crystallinity of the resin can be cited as a factor in hydrolysis. Since hydrolysis progresses more easily in amorphous regions than in crystalline regions, hydrolysis can be suppressed by increasing crystallinity.
• an additive or the like is added to a thermoplastic resin composition, the particles become crystal nuclei and promote the formation of crystals (nucleation effect), thereby improving crystallinity and providing an effect of inhibiting hydrolysis.
• thermoplastic resin composition for agricultural materials of this embodiment contains specific amounts of starch (A) that promotes biodegradability and viscosity modifier (C) that increases melt tension
• agricultural materials made of the resin composition The biodegradation rate of can be adjusted.
• the decomposition of agricultural materials is suppressed and their shape can be maintained for at least the 4 months of the seed and seedling growing period, and about a year after the seeding and seedling growing period has passed, the agricultural materials are absorbed by the microorganisms in the soil. It is desirable that the soil has been decomposed by water and can be dug into the soil.
• Starch (A) Starch (A) promotes the action (biodegradability) of various microorganisms present in soil or water.
• Starch (A) is not particularly limited, and commonly available starches can be used. Examples include corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, and the like.
• corn starch which has a uniform particle size of about 20 ⁇ m, can make the thickness of agricultural materials made of resin compositions uniform (reducing surface irregularities) and suppressing the occurrence of thin parts. This is preferable because damage to agricultural materials can be suppressed as a result. These may be used alone or in combination of two or more.
• Starch (A) is a component that can adjust the biodegradation rate, and its content is preferably 5 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight in 100 parts by weight of the resin composition. parts, or 10 to 30 parts by mass.
• content of starch (A) is 5 parts by mass or more, biodegradation is promoted, and when it is 60 parts by mass or less, the content of biodegradable resin (B) can be ensured to ensure moldability. can.
• the average particle size of starch (A) is preferably 5 to 50 ⁇ m, and may be 10 to 50 ⁇ m.
• the average particle size of starch (A) in the resin composition contributes to moldability, so the average particle size of starch (A) is Preferably, the range is within the range.
• the average particle size of starch (A) can be determined by, for example, observing the particles of starch (A) using a scanning electron microscope, observing 100 particles at random, and measuring the two most distant points on the outer shape of each particle. The distance between the two can be measured based on the length of the micron marker on the screen and averaged.
• Biodegradable resin (B) The biodegradable resin (B) is decomposed by the action of various microorganisms present in soil or water.
• the biodegradable resin (B) is not particularly limited, and commonly available biodegradable resins can be used. Examples include polycaprolactone, aliphatic polyester resin, and aliphatic aromatic polyester resin. These biodegradable resins may be used alone or in combination of two or more.
• aliphatic polyester resins or aliphatic aromatic polyester resins are preferred from the viewpoint of biodegradability and moldability.
• the content of aliphatic polyester resin must be greater than or equal to the content of aliphatic aromatic polyester resin. preferable.
• the content ratio (parts by mass) of aliphatic polyester resin and aliphatic aromatic polyester resin is, for example, preferably 1 to 4:1, more preferably 1 to 3:1, and 1 to 3:1.
• the ratio is more preferably 1 to 2:1, particularly preferably 1 to 1.65:1, even more preferably 1 to 1.57:1, and even more preferably 1.5 to 2:1. Good too.
• Examples of the aliphatic polyester resin include aliphatic polyester obtained by polycondensation reaction of an aliphatic diol and aliphatic dicarboxylic acid, and polylactic acid obtained by polycondensation of lactic acid.
• Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4- Examples include cyclohexanedimethanol. These may be used alone, or a mixture thereof may be used. Among them, it is preferable to use 1,4-butanediol.
• aliphatic dicarboxylic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides that are derivatives thereof may also be used.
• succinic acid, succinic anhydride, or a mixture of these and adipic acid is preferred.
• polybutylene succinate (PBS) obtained from 1,4 butanediol and succinic acid (for example, "BioPBS" (trade name) manufactured by PPT MCC Biochem), polybutylene obtained by copolymerizing adipic acid with PBS
• PBS polybutylene succinate
• PBSA succinate adipate
• Examples of the aliphatic aromatic polyester resin include copolymers containing aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and chain aliphatic and/or alicyclic diol units.
• the diol component providing the diol unit usually has 2 to 10 carbon atoms, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, etc. .
• diols having 2 to 4 carbon atoms are preferred, ethylene glycol and 1,4-butanediol are more preferred, and 1,4-butanediol is even more preferred.
• the dicarboxylic acid component that provides the dicarboxylic acid unit usually has 2 to 10 carbon atoms, and includes, for example, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like. Among these, succinic acid or adipic acid is preferred.
• the aromatic dicarboxylic acid component that provides aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.
• PBAT polybutylene adipate terephthalate
• PBAT polybutylene adipate terephthalate
• the biodegradable resin (B) may be in the form of a combination of the above aliphatic polyester resin and/or aliphatic aromatic polyester resin and other biodegradable resins.
• Other biodegradable resins include poly(3-hydroxyalkanoate), an aliphatic polyester copolymer obtained from hydroxyalkanoic acid and polycarboxylic acid (especially poly(3-hydroxybutyrate)). co-3-hydroxyhexanoate) (PHBH) (for example, "Aonilex” (trade name) manufactured by Kaneka Corporation), polylactic acid (PLA) (for example, "REVODE” (trade name) manufactured by Kaisho Biological Materials Co., Ltd.), For example, "Ingeo” (trade name) manufactured by Nature Works.
• the content of the biodegradable resin (B) may be 35 to 95 parts by mass, more preferably 35 to 94.99 parts by mass, and 35 to 94.5 parts by mass in 100 parts by mass of the resin composition. It is more preferably 39 to 90 parts by weight, and even more preferably 39 to 90 parts by weight.
• the total content of the aliphatic polyester resin and/or the aliphatic aromatic polyester resin is preferably 80 parts by mass or more, and 90 parts by mass in 100 parts by mass of the biodegradable resin (B). It is more preferable that it is above.
• the viscosity modifier (C) adjusts the viscosity of the resin composition to improve moldability, and increases the melt tension of the resin composition, which is an indicator of moldability.
• the viscosity modifier (C) is not particularly limited, and commonly available ones can be used. Examples include carbodiimide compounds, oxazoline compounds, epoxy compounds, acid anhydride compounds, cellulose fibers, silica fillers, and the like.
• the melt tension of the resin composition can be increased.
• the polyfunctional compound include polyfunctional carbodiimide compounds, polyfunctional oxazoline compounds, epoxy compounds, acid anhydride compounds, and the like.
• the polyfunctional carbodiimide compound may be a monomer or polymer having two or more carbodiimide groups, but preferably a polymer having two or more carbodiimide groups.
• a reactive compound is used as the viscosity modifier (C) to introduce a reactive group into the biodegradable resin (B), and a crosslinked structure is formed using this reactive group as a starting point, thereby increasing the melt tension of the resin composition. can be raised.
• the reactive compound include carbodiimide compounds, oxazoline compounds, epoxy compounds, acid anhydride compounds, and the like. 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 filler may be either an organic filler or an inorganic filler, and examples thereof include cellulose fibers and silica fillers.
• CMF cellulose microfibers
• CDI carbodiimide compounds
• Cellulose microfiber is a relatively large size obtained by reducing the fibrillation process in cellulose, which is obtained by treating pulp with hot water, etc., hydrolyzing it to make it brittle, and then defibrating it using a crushing method such as a high-pressure homogenizer.
• a crushing method such as a high-pressure homogenizer.
• cellulose fibers By including cellulose microfibers and a carbodiimide compound, the viscosity of the resin composition can be increased and strength can be ensured.
• the strength of the resin composition increases due to the filler effect of the cellulose microfibers.
• the silica filler has a filler effect like cellulose microfibers, it increases the strength of the resin composition like cellulose microfibers.
• blow molding can be used to mold the resin composition containing at least one of cellulose microfibers and silica filler as the viscosity modifier (C).
• a carbodiimide compound When a carbodiimide compound is contained in a resin composition, the resin and carbodiimide compound react and the molecular weight of the resin increases, so it takes time for the resin to be hydrolyzed and its molecular weight decreases, resulting in a slow biodegradation rate. Become. Therefore, in the case of agricultural materials where the strength of the resin composition is required, it is preferable that a carbodiimide compound is included as the viscosity modifier (C).
• C viscosity modifier
• oxazoline compounds, epoxy compounds, and acid anhydride compounds each have reactivity with resins similarly to carbodiimide compounds, each of 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 using, for example, vacuum molding.
• carbodiimide compounds include polycarbodiimide compounds such as "Carbodilite HMV-15CA (trade name)” manufactured by Nisshinbo Chemical; dicyclohexylcarbodiimide, diphenylcarbodiimide, di- ⁇ -naphthylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, and dioxylcarbodiimide; Chill Examples include monocarbodiimides such as carbodiimide, t-butylisopropylcarbodiimide, and di-t-butylcarbodiimide; cyclic carbodiimide compounds such as "Carbodista TCC-NP" (trade name) manufactured by Teijin Ltd.; These compounds may be used alone or in combination.
• Polycarbodiimide compounds such as "Carbodilite HMV-15CA (trade name)” manufactured by Nisshinbo Chemical
• Examples of the oxazoline compound include “Epocross RA-45” (trade name) and “Epocross RPS-1005" (trade name) manufactured by Nippon Shokubai Co., Ltd. These compounds may be used alone or in combination.
• Examples of the epoxy compound include epoxy-acrylic compounds ("Joncryl ADR-4468” (trade name) manufactured by BASF, “Joncryl ADR-4400” (trade name) manufactured by BASF, "Alphon UG” manufactured by Toagosei Co., Ltd. -4040'' (trade name), and ⁇ Alfon UG-4070'' (trade name) manufactured by Toagosei Co., Ltd. These compounds may be used alone or in combination.
• acid anhydride compounds examples include styrene maleic anhydride compounds (PALMER HOLLAND's "XIBOND120” (product name), “XIBOND140” (product name), “XIBOND160” (product name), “XIBOND180” (product name) , “XIBOND200” (product name), “XIBOND220” (product name), “XIBOND250” (product name), “XIBOND280” (product name), Tomoe Kogyo Co., Ltd.
• silica-based fillers include silica fillers ("Aerosil 130" (product name), “Aerosil 150” (product name), “Aerosil 200” (product name), and “Aerosil 300” (product name) manufactured by Nippon Aerosil Co., Ltd.
• the content of the viscosity modifier (C) is preferably 0.01 to 3 parts by mass in 100 parts by mass of the resin composition, and 0.01 to 3 parts by mass, in order to adjust the viscosity of the resin composition to an appropriate value.
• the amount is more preferably 2 parts by weight, and may be 0.01 to 1 part by weight, or 0.1 to 0.8 parts by weight.
• the content of the cellulose fibers is preferably 0 parts by mass or more and less than 1.5 parts by mass, and 0.01 to 1.5 parts by mass in 100 parts by mass of the resin composition.
• the amount is preferably 4 parts by weight, more preferably 0.01 to 1.2 parts by weight, and even more preferably 0.01 to 1 part by weight.
• thermoplastic resin composition for agricultural materials of this embodiment does not contain a plasticizer (D) that is normally used for plasticizing starch (A).
• a plasticizer (D) that is normally used for plasticizing starch (A).
• not containing a plasticizer (D) means that the plasticizer (D) is not substantially contained, and specifically, the content of the plasticizer (D) is This means 0 to 5 parts by weight based on 100 parts by weight of the composition.
• plasticizer (D) examples include alcohol, which is an organic compound having a hydroxyl group. Specific examples include glycerin, glycerin monoester, ethylene glycol, and diethylene glycol.
• the amount of plasticizer (D) is 5 parts by mass or less based on 100 parts by mass of the resin composition, the resulting molded product can have good moldability while suppressing stickiness on the surface.
• the content of the plasticizer (D) is preferably 0 to 2 parts by mass, more preferably 0 to 1 part by mass, based on 100 parts by mass of the resin composition. , 0 parts by mass (not included) is more preferable.
• the resin composition can optionally contain components such as other additives (excluding the plasticizer (D)) as necessary.
• Other additives include, for example, dispersants, lubricants (higher fatty acid metal salts, waxes, etc.), hydrotalcite, surfactants, antistatic agents, flame retardants, antioxidants, ultraviolet absorbers, fillers, Examples include pigments.
• the selection of other optional components and the amounts used thereof are not particularly limited as long as they are within the range that can solve the problems of one embodiment of the present invention. Multiple additives may be used in combination.
• the resin composition may partially contain a resin other than the biodegradable resin within a range that does not impede the effects of one embodiment of the present invention.
• Pigments are not particularly limited and commonly available pigments can be used, but from the viewpoint of the natural environment, pigments such as cadmium, lead, chromium, arsenic, mercury, copper, selenium, nickel, molybdenum, and fluorine are recommended. Preferably, it does not substantially contain pigments containing.
• the resin composition contains a pigment
• a dispersant for dispersing the pigment examples include fatty acid metal salts.
• the fatty acid component of the fatty acid metal salt is preferably a chain carboxylic acid having 6 to 30 carbon atoms, and may be linear or branched, and may have only saturated bonds or unsaturated bonds.
• Examples of fatty acids include, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, behenic acid, oleic acid, erucic acid, linoleic acid, montanic acid, etc.
• the metal elements of Group 1, Group 2, Group 12, and Group 13 are preferable, and elements of Group 1 or Group 2 are more preferable. Specific examples include sodium, potassium, calcium, magnesium, barium, and the like.
• fatty acid metal salts examples include calcium stearate, magnesium stearate, barium stearate, calcium laurate, magnesium laurate, sodium montanate, and the like. These may be used alone or in combination of two or more. Among these, calcium stearate, magnesium stearate, calcium laurate, and magnesium laurate are preferred.
• thermoplastic resin composition for agricultural materials the processability during extrusion is such that strand breakage occurs no more than 5 times during continuous production for 1 hour, and may occur 1 to 5 times. It is preferable that no cuts occur.
• the melt viscosity at a shear rate of 243 s -1 according to JIS K7199:1999 is such that the molded product obtained at a temperature above the melting point of the biodegradable resin (B) and below the melting point + 40 ° C. From the viewpoint of the strength of the resin composition and the fluidity and moldability of the resin composition, it is 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.
• thermoplastic resin composition for agricultural materials according to this embodiment can be used for various agricultural materials.
• this resin composition can be suitably used for pots for raising seedlings.
• a seedling raising pot is a pot used to grow seedlings in a container until they reach a certain level of growth, rather than directly sowing seeds in a field.
• the molded product using the resin composition of this embodiment biodegrades appropriately in the soil, so there is no need to take out the seedlings from the seedling pot and transplant them after they have grown, and they can be placed in the soil as they are in the seedling pot.
• Portable
• the resin composition of this embodiment can be produced by kneading starch (A) and viscosity modifier (C) at a temperature at which biodegradable resin (B) melts.
• the biodegradable resin (B), starch (A), viscosity modifier (C), and various additives are added as necessary, and the mixture is mixed in a kneader, roll mill, super mixer, or high speed.
• the resin composition can be in the form of granules or beads. It is preferable to use a single-screw extruder or a twin-screw extruder to form pellets because the kneading force is strong and the subsequent molding process is easy.
• the resin composition may be used in the form of either a masterbatch or a compound.
• a masterbatch after the masterbatch is manufactured, the same biodegradable resin (B) used for the manufacture of the masterbatch is used as a diluent resin as the main resin for agricultural materials, for example, and the masterbatch is blended to produce agricultural materials. Materials can be manufactured.
• the content of the masterbatch is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the biodegradable resin (B) as the main resin. .
• the biodegradable resin (B) used as the diluent resin at this time may be the same as or different from that used for manufacturing the masterbatch, but it is better to use the same biodegradable resin. This is preferred because the thermoplastic resin composition and the resin have excellent compatibility. In the case of a compound, after producing the compound, the compound can be used as is to produce agricultural materials in the manner described above.
• the agricultural materials of this embodiment can be obtained by molding the above-mentioned thermoplastic resin composition for agricultural materials.
• Examples of agricultural materials include seedling pots, mulch films, containers, and agricultural nets.
• a seedling growing pot is a container used for the purpose mentioned above.
• the molding method for the seedling growing pot is not particularly limited, but examples include blow molding, extruding a heated and plasticized resin composition, directly putting it in a mold without cooling and solidifying it, and blowing air through it, and heating. Also suitable is vacuum forming, in which a sheet or film of a plasticized resin composition is placed on a mold and vacuum suction is applied from inside the mold.
• Seedling pots made of the above-mentioned resin composition biodegrade after being buried in the soil, so they do not harm the natural environment and can reduce the hassle of removing seeds and seedlings from seedling pots and sowing them. can.
• the seedling growing pot can be successfully grown without being decomposed for about 4 months, which is the growing period for seedlings.
• this seedling-raising pot has strength suitable for seedling-raising purposes, so it is easy to handle and can maintain an appropriate shape during the seedling-raising period.
• Multi film Mulching film is a film that covers the roots of crops.
• the method for molding a film from the above-mentioned resin composition is not particularly limited, but may include extrusion molding in which a film extruded through a T-die using an extruder is cooled and solidified with a cast roll, or a method in which molding is performed using an inflation molding machine. is suitable.
• the resin composition of this embodiment can be blow-molded, and for example, when three sets of two seedling-growing pots are successively produced using a direct blow molding machine, one seedling-growing pot of the first set is The difference between the weight per seedling-growing pot in the third set and the weight per seedling-growing pot in the first set can be made less than 30% of the weight per seedling-growing pot in the first set. Further, the weight per seedling growing 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. By using the above resin composition, blow moldability can be obtained.
• the molded product is a seedling growing pot
• the above resin composition it is possible to obtain a seedling growing pot with ensured strength.
• the fragility of the seedling pot is determined if less than 3 out of 10 seedling pots are broken when 1 kg of soil is placed in the pot and dropped from a height of 5 m. In most cases, the number of broken pieces may be 1 to 3 or less out of 10, and it is preferable that none of them be broken.
• the dynamic friction coefficient ⁇ D of the surface of a molded article molded using the above-mentioned resin composition according to JIS K7125 may be less than 0.5, may be 0.3 or more and less than 0.5, and is less than 0.3. It is preferable. By using the above resin composition, a molded article with suppressed stickiness can be obtained.
• the thermoplastic resin composition for agricultural materials contains a specific amount of starch (A) that promotes biodegradability and a viscosity modifier (C) that increases melt tension, and a plasticizer (D). ), it is possible to obtain agricultural materials with excellent biodegradability and moldability, and with suppressed surface stickiness.
• thermoplastic resin composition for agricultural materials that contains starch (A), a biodegradable resin (B), and a viscosity modifier (C), and does not contain a plasticizer (D).
• the content of the starch (A) is 5 to 60 parts by mass in 100 parts by mass of the thermoplastic resin composition for agricultural materials
• the content of the viscosity modifier (C) is the thermoplastic resin composition for agricultural materials.
• a thermoplastic resin composition for agricultural materials in an amount of 0.01 to 1 part by mass per 100 parts by mass.
• the biodegradable resin (B) includes an aliphatic polyester resin and an aliphatic aromatic polyester resin, and the content of the aliphatic polyester resin is equal to or less than the aliphatic aromatic polyester resin.
• the melt viscosity at a shear rate of 243 s -1 is 1000 Pa ⁇ s or more and less than 5000 Pa ⁇ s at a temperature not lower than the melting point of the biodegradable resin (B) and not higher than the melting point +40°C, [1] to [5] ]
• the thermoplastic resin composition for agricultural materials according to any one of [1] to [6] which is used for blow molding or vacuum forming.
• the thermoplastic resin composition for agricultural materials according to any one of [1] to [7] which is for use in pots for raising seedlings.
• Agricultural materials comprising the thermoplastic resin composition for agricultural materials described in [1] to [7] above.
• the agricultural material according to [9] which is a seedling-raising pot.
• a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.
• the present invention relates to the subject matter of Japanese Patent Application No. 2022-053396 filed March 29, 2022, the entire disclosure of which is incorporated herein by reference.
• ⁇ Average particle size measurement> Starch particles were observed using a scanning electron microscope (SEM) manufactured by Hitachi, Ltd. at a field magnification of 100 times, and 100 particles were randomly observed. The distance between the points was measured based on the length of the micron marker on the screen, and the distance was averaged.
• SEM scanning electron microscope
• thermoplastic resin composition for agricultural materials.
• A-1 Chemister 420 (manufactured by Glico Nutritional Foods, corn-derived starch, average particle size: 15 ⁇ m)
• A-2 Chemister 310 (manufactured by Glico Nutritional Foods, cassava-derived starch, average particle size: 50 ⁇ m)
• A-3 FP (manufactured by Glico Nutritional Foods, potato-derived starch, average particle size: 100 ⁇ m)
• C-1 KC flock W-50 (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 Ltd., cyclic carbodiimide compound)
• C-4 Joncryl ADR-4468 (manufactured by BASF, epoxy-acrylic compound)
• C-5 XIBOND220 (manufactured by PALMER HOLLAND, styrene maleic anhydride compound)
• C-6 Epocross RA-45 (manufactured by Nippon Shokubai Co., Ltd., oxazoline compound)
• C-7 Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd., silica filler)
• C-8 Nip seal SS-50 (manufactured by To
• thermoplastic resin composition for agricultural materials 5 parts by mass of (A-1) as starch (A), 94.5 parts by mass of (B-1) as biodegradable resin (B), 0.5 parts by mass of (C-1) as viscosity modifier (C) were mixed, extruded at 190°C using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), and granulated to obtain a thermoplastic resin composition for agricultural materials.
• thermoplastic resin composition for agricultural materials was blow molded or vacuum molded to obtain a seedling growing pot.
• thermoplastic resin composition for agricultural materials and a pot for raising seedlings were obtained in the same manner as in Experimental Example 1, except that the materials and amounts (parts by mass) shown in Table 1 were changed.
• Experimental Examples 1 to 13 have a structure containing only one of the aliphatic polyester resin (B-1 or B-3) and the aliphatic aromatic polyester resin (B-2) as the biodegradable resin, and the aliphatic This can be treated as a reference example in distinction from an experimental example in which a polyester resin (B-1 or B-3) and an aliphatic aromatic polyester resin (B-2) are used together as a biodegradable resin.
• thermoplastic resin compositions for agricultural materials and seedling growing pots obtained in the experimental examples and comparative examples were evaluated based on the following criteria. The evaluation results are shown in Table 1.
• thermoplastic resin compositions for agricultural materials during extrusion were evaluated.
• the evaluation criteria were as follows, and ⁇ and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : Strand breakage does not occur during continuous production for 1 hour. ⁇ : Strand breakage occurs 1 to 5 times during continuous production for 1 hour. ⁇ : Strand breakage occurs 6 or more times during continuous production for 1 hour.
• melt viscosity evaluation> The melt viscosity of the thermoplastic resin composition for agricultural materials was measured at 150° C. and a shear rate of 243 s ⁇ 1 in accordance with JIS K7199:1999. The evaluation criteria were as follows, and ⁇ and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : Melt viscosity is 1500 Pa ⁇ s or more ⁇ : Melt viscosity is 1000 to less than 1500 Pa ⁇ s ⁇ : Melt viscosity is less than 1000 Pa ⁇ s
• ⁇ Blow moldability evaluation> Using a direct blow molding machine (manufactured by Nippon Placon Co., Ltd.), three sets of two seedling pots were made in succession at 150°C, and the weight per seedling pot of the first set and the weight of the third set of seedling pots were calculated. The difference in weight per seedling pot (weight difference) and the weight per seedling growing pot were evaluated as formability during production. In this evaluation, "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 were as follows, and ⁇ , ⁇ , and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : Blow molding is possible, and the weight per seedling growing pot is 0.9 g or more.
• Blow molding is possible, and the weight per seedling growing pot is 0.8 g or more and less than 0.9 g.
• ⁇ : Blow molding is possible, and the weight of each seedling growing pot is 0.8 g or more and less than 0.9 g.
• Weight per pot is 0.7g or more and less than 0.8g ⁇ : 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 formed sheet was heated to 110° C., and a seedling growing pot was formed using a vacuum forming machine, and the formability during production was evaluated.
• the evaluation criteria were as follows, and ⁇ , ⁇ , and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : Vacuum forming is possible, and the seedling growing pot has no defective appearance due to sagging. ⁇ : Vacuum forming is possible, and there is a slight appearance defect in the seedling pot due to sagging. ⁇ : Vacuum forming is possible, and a defective appearance due to sagging can be observed in the seedling pot. ⁇ : Vacuum forming is not possible.
• the evaluation criteria were as follows, and ⁇ and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : The seedling growing pot is free-standing without bending. ⁇ : Deflection occurs in the seedling growing pot, but it stands on its own. ⁇ : The seedling growing pot cannot stand up to its own weight and cannot stand on its own.
• ⁇ Molded product brittleness evaluation> The fragility of the seedling growing pots was evaluated by placing 1 kg of soil in each of the 10 seedling growing pots prepared during the vacuum formability evaluation and dropping the pots from a height of 5 m.
• the evaluation criteria were as follows, and ⁇ and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : None of the seedling pots out of 10 were destroyed. ⁇ : 1 to 3 out of 10 were destroyed. ⁇ : 4 or more out of 10 were destroyed.
• ⁇ Molded product stickiness evaluation> The stickiness of the seedling growing pot was evaluated by measuring the dynamic friction coefficient of the side surface of the seedling growing pot prepared at the time of blow moldability evaluation according to JIS K7125.
• the evaluation criteria were as follows, and ⁇ and ⁇ were considered to be practical. [Evaluation criteria] ⁇ : Dynamic friction coefficient ⁇ D is less than 0.3 ⁇ : Dynamic friction coefficient ⁇ D is 0.3 or more and less than 0.5 ⁇ : Dynamic friction coefficient ⁇ D is 0.5 or more

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